US10513774B2 - Substrate processing apparatus and guide portion - Google Patents

Abstract

A cleaning method includes (a) providing a process chamber after forming an oxide film on a substrate in the process chamber formed by a reaction tube and a manifold supporting the reaction tube by performing a cycle a predetermined number of times, the cycle including supplying a source gas to the substrate through a first nozzle in the manifold extending upward to an inside of the reaction tube, and supplying an oxidizing gas to the substrate through a second nozzle in the manifold extending upward to the inside of the reaction tube; and (b) cleaning an inside of the process chamber. The step (b) includes a first cleaning process of supplying a hydrogen fluoride gas into the reaction tube through the second nozzle; and a second cleaning process of supplying a hydrogen fluoride gas onto an inner wall surface of the manifold through a third nozzle disposed in the manifold.

Description

CROSS-REFERENCE TO RELATED PATENT APPLICATION

This U.S. non-provisional patent application and is a division of U.S. patent application Ser. No. 14/223,132 filed on Mar. 24, 2014 now U.S. Pat. No. 9,401,272, and claims priority under 35 U.S.C. § 119 of Japanese Patent Applications No. 2013-061907 and No. 2014-039468 filed on Mar. 25, 2013 and Feb. 28, 2014, respectively, in the Japanese Patent Office, the entire contents of which are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a cleaning method, a method of manufacturing a semiconductor device, a substrate processing apparatus and a non-transitory computer-readable recording medium.

2. Description of the Related Art

As a method of cleaning an inside of a process chamber of a substrate processing apparatus, there is a cleaning method performed by supplying a cleaning gas into a process chamber through a nozzle configured to supply a processing gas for processing a substrate.

SUMMARY OF THE INVENTION

However, since a nozzle configured to supply a processing gas is often disposed so as to supply a gas toward a substrate, it is difficult to clean other portions, for example, the vicinity of an opening for unloading and unloading the substrate. Reaction by-products are likely to remain in the portions in which cleaning is difficult. In order to remove the reaction by-products, a cleaning gas needs to be supplied for a long time or further cleaning needs to be performed manually by wiping and the like when cleaning using a gas is not sufficient. Thereby, there is a problem in that a time required for cleaning increases.

An object of the present invention is to provide technology capable of reducing a time required for cleaning.

According to an aspect of the present invention, there is provided a cleaning method, including:

(a) providing a process chamber after forming an oxide film on a substrate in the process chamber formed by a reaction tube and a manifold supporting the reaction tube by performing a cycle a predetermined number of times, the cycle including supplying a source gas to the substrate in the process chamber through a first nozzle disposed in the manifold and extending upward from the manifold to an inside of the reaction tube, and supplying an oxidizing gas to the substrate in the process chamber through a second nozzle disposed in the manifold and extending upward from the manifold to the inside of the reaction tube; and

(b) cleaning an inside of the process chamber,

wherein the step (b) includes:

a first cleaning process of supplying a hydrogen fluoride gas into the reaction tube through the second nozzle; and

a second cleaning process of supplying a hydrogen fluoride gas onto an inner wall surface of the manifold through a third nozzle disposed in the manifold.

According to another aspect of the present invention, there is provided a method of manufacturing a semiconductor device, including:

(a) forming an oxide film on a substrate in the process chamber formed by a reaction tube and a manifold supporting the reaction tube by performing a cycle a predetermined number of times, the cycle including supplying a source gas to the substrate in the process chamber through a first nozzle disposed in the manifold and extending upward from the manifold to an inside of the reaction tube, and supplying an oxidizing gas to the substrate in the process chamber through a second nozzle disposed in the manifold and extending upward from the manifold to the inside of the reaction tube; and

(b) cleaning an inside of the process chamber after the step (a) is performed,

wherein the step (b) includes:

a first cleaning process of supplying a hydrogen fluoride gas into the reaction tube through the second nozzle; and

a second cleaning process of supplying a hydrogen fluoride gas onto an inner wall surface of the manifold through a third nozzle disposed in the manifold.

According to still another aspect of the present invention, there is provided a substrate processing apparatus, including:

a process chamber formed by a reaction tube and a manifold supporting the reaction tube;

a source gas supply system configured to supply a source gas into the process chamber;

an oxidizing gas supply system configured to supply an oxidizing gas into the process chamber;

a hydrogen fluoride gas supply system configured to supply a hydrogen fluoride gas into the process chamber;

a first nozzle disposed in the manifold and extending upward from the manifold to an inside of the reaction tube;

a second nozzle disposed in the manifold and extending upward from the manifold to the inside of the reaction tube;

a third nozzle disposed in the manifold; and

a control unit configured to control the source gas supply system, the oxidizing gas supply system and the hydrogen fluoride gas supply system to perform: (a) forming an oxide film on a substrate in the process chamber by performing a cycle a predetermined number of times, the cycle including supplying the source gas to the substrate in the process chamber through the first nozzle and supplying the oxidizing gas to the substrate in the process chamber through the second nozzle; and (b) cleaning an inside of the process chamber after performing the step (a), wherein the step (b) includes a first cleaning process of supplying the hydrogen fluoride gas into the reaction tube through the second nozzle and a second cleaning process of supplying the hydrogen fluoride gas onto an inner wall surface of the manifold through the third nozzle.

According to yet another aspect of the present invention, there is provided a non-transitory computer-readable recording medium storing a program causing a computer to execute:

(a) forming an oxide film on a substrate in the process chamber formed by a reaction tube and a manifold supporting the reaction tube by performing a cycle a predetermined number of times, the cycle including supplying a source gas to the substrate in the process chamber through a first nozzle disposed in the manifold and extending upward from the manifold to an inside of the reaction tube, and supplying an oxidizing gas to the substrate in the process chamber through a second nozzle disposed in the manifold and extending upward from the manifold to the inside of the reaction tube; and

(b) cleaning an inside of the process chamber after the step (a) is performed,

wherein the step (b) includes:

a first cleaning process of supplying a hydrogen fluoride gas into the reaction tube through the second nozzle; and

a second cleaning process of supplying a hydrogen fluoride gas onto an inner wall surface of the manifold through a third nozzle disposed in the manifold.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic configuration diagram illustrating a vertical processing furnace of a substrate processing apparatus preferably used in an embodiment of the present invention and is a vertical cross-sectional view illustrating a processing furnace part.

FIG. 2 is an enlarged partial cross-sectional view illustrating a periphery of anozzle40bin a first embodiment of the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention.

FIG. 3 is a schematic configuration diagram illustrating the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention and is a cross-sectional view illustrating the processing furnace part taken along the line A-A ofFIG. 1.

FIG. 4 is a schematic configuration diagram illustrating a controller of the substrate processing apparatus preferably used in the embodiment of the present invention and is a block diagram illustrating a control system of the controller.

FIG. 5 is a flowchart illustrating a substrate processing process of the present invention.

FIG. 6 is a diagram illustrating a timing of supplying a gas in a film-forming sequence of the present invention.

FIG. 7 is a diagram illustrating a timing of supplying a cleaning gas when cleaning is performed.

FIGS. 8aand 8bare diagrams illustrating a cleaning method according to a temperature range in the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention.

FIG. 9 is an enlarged partial cross-sectional view illustrating a periphery of anozzle320bin a second embodiment of the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention.

FIG. 10 is an enlarged partial cross-sectional view illustrating a periphery of anozzle330bin a third embodiment of the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention.

FIG. 11 is an enlarged partial cross-sectional view illustrating a periphery of anozzle340bin a fourth embodiment of the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention.

FIG. 12 is an enlarged partial cross-sectional view illustrating a periphery of anozzle350bin a fifth embodiment of the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention.

FIG. 13 is an enlarged partial cross-sectional view illustrating a periphery of anozzle360bin a sixth embodiment of the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention.

FIG. 14 is an enlarged partial cross-sectional view illustrating a periphery of anozzle40bin a seventh embodiment of the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention.

FIG. 15 is an enlarged partial cross-sectional view illustrating a periphery of anozzle40bin an eighth embodiment of the vertical processing furnace of the substrate processing apparatus preferably used in the embodiment of the present invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTSFirst Embodiment

The first embodiment of the present invention will be described.

(1) Configuration of Substrate Processing Apparatus

Aprocessing furnace12 includes aheater14 serving as a heating unit (heating mechanism). Theheater14 has a cylindrical shape and is vertically installed by being supported by a heater base (not illustrated) serving as a holding plate. Theheater14 also functions as an activating mechanism (excitation unit) for activating a gas by heat.

In theheater14, areaction tube16 is concentrically provided with respect to theheater14. Thereaction tube16 is formed to have a cylindrical shape whose upper end is blocked and lower end is opened. Thereaction tube16 is made of a heat-resistant material such as quartz (SiO₂) and silicon carbide (SiC).

A manifold18 (inlet flange) is concentrically provided with respect to thereaction tube16 below thereaction tube16. The manifold18 is formed to have a cylindrical shape whose upper end and lower end are opened and is made of a metal such as stainless. An upper end of the manifold18 is engaged with a lower end of thereaction tube16 and is configured to support thereaction tube16.

AnO ring20ais provided as a seal member between the manifold18 and thereaction tube16. The manifold18 is supported by the heater base, and thereby thereaction tube16 is in a vertically installed state.

A process container (reaction container) mainly includes thereaction tube16 and the manifold18. Aprocess chamber22 is formed in a cylindrical hollow portion of the process container. An opening for loading and unloading awafer24 as a substrate is formed below theprocess chamber22. Theprocess chamber22 uses aboat28 as a substrate holder for holding thewafer24 to accommodate thewafer24 in a vertical arrangement of multiple stages in a horizontal posture.

Theboat28 holds a plurality ofwafers24 in multiple stages in vertical and central alignment. Theboat28 is made of a heat-resistant material such as quartz and SiC. Aninsulation member30 made of a heat-resistant material such as quartz and SiC is provided in a bottom of theboat28 and is configured such that heat from theheater14 is not easily delivered to a lower part. Theinsulation member30 may include a plurality of heat insulating plates made of a heat-resistant material such as quartz and SiC and a heat insulating plate holder for horizontally supporting these heat insulating plates in multiple stages.

Theprocessing furnace12 includes a firstgas supply system32 configured to supply a first gas (for example, a source gas) for processing thewafer24 into theprocess chamber22, a secondgas supply system34 configured to supply a second gas (for example, a reaction gas) for processing thewafer24 into theprocess chamber22, and a thirdgas supply system36 configured to supply a third gas (a cleaning gas) for cleaning an inside of theprocess chamber22.

Theprocessing furnace12 includes threenozzles40a,40b, and40cfor introducing gases into theprocess chamber22. Thesenozzles40a,40b, and40care provided so as to penetrate a sidewall of the manifold18. Thenozzles40a,40b, and40care made of a heat-resistant material such as quartz and SiC. Agas supply pipe42aand an inertgas supply pipe52aare connected to thenozzle40a. A cleaninggas supply pipe62band an inertgas supply pipe52bare connected to thenozzle40b. Agas supply pipe42c, an inertgas supply pipe52c, a cleaninggas supply pipe62a, agas supply pipe42d, and an inertgas supply pipe52dare connected to thenozzle40c.

In this manner, theprocessing furnace12 includes the three nozzles [thenozzles40a,40b, and40c], the three gas supply pipes [thegas supply pipes42a,42c, and42d], the four inert gas supply pipes [the inertgas supply pipes52a,52b,52c, and52d], and the two cleaning gas supply pipes [the cleaninggas supply pipes62aand62b]. A plurality of types of gases are supplied into theprocess chamber22.

(Source Gas Supply System: First Gas Supply System)

In thegas supply pipe42a, when a side of theprocess chamber22 is set as a downstream side, in order from an upstream end, a mass flow controller (MFC)44aserving as a flow rate controller (flow rate control unit) and avalve46aserving as an on-off valve are provided, and the inertgas supply pipe52ais connected to a downstream side of thevalve46a. Thenozzle40ais connected to a front end of thegas supply pipe42a. In order from an upstream end, anMFC54aand avalve56aare provided in the inertgas supply pipe52a.

Thenozzle40ais provided in a toric space between an inner wall of thereaction tube16 and thewafer24 accommodated in theprocess chamber22, and is provided so as to extend upward in a stacking direction of thewafer24 from the manifold18 to an inside of thereaction tube16. Thenozzle40ais provided so as to follow a region that is a side of a wafer arrangement region in which thewafer24 is arranged and that horizontally surrounds the wafer arrangement region. Thenozzle40ais configured as an L-shaped long nozzle. Thenozzle40ais provided such that a horizontal portion thereof penetrates a sidewall of the manifold18 and a vertical portion thereof extends upward from at least one end side of the wafer arrangement region toward the other end side

Agas supply hole48aconfigured to supply a gas is provided in a side surface of thenozzle40a. Thegas supply hole48afaces a center of thereaction tube16 and is configured to supply a gas toward thewafer24 accommodated in theprocess chamber22. A plurality of gas supply holes48aare provided from a bottom to a top of thereaction tube16 at the same pitch, and each have the same opening area.

The firstgas supply system32 mainly includes thegas supply pipe42a, theMFC44a, and thevalve46a. Thenozzle40aalso functions as a part of the firstgas supply system32. Also, an inert gas supply system mainly includes the inertgas supply pipe52a, theMFC54a, and thevalve56a. The inert gas supply system also functions as a purge gas supply system.

A source gas containing a predetermined element and a halogen element is supplied from thegas supply pipe42a. As a source gas (a gas containing Si and Cl) which contains silicon (Si) as the predetermined element and chlorine (Cl) as the halogen element, for example, a hexachlorodisilane (Si₂Cl₆, abbreviated to HCDS) gas, which is a kind of chlorosilane-based source gas, is supplied from thegas supply pipe42ainto theprocess chamber22 through theMFC44a, thevalve46a, and thenozzle40a. At this time, an inert gas may also be supplied from the inertgas supply pipe52ainto thegas supply pipe42athrough theMFC54aand thevalve56a.

In the present embodiment, the firstgas supply system32 functions as a source gas supply system.

The chlorosilane-based source gas refers to a chlorosilane-based material in a gas state, for example, a gas obtained by vaporizing a chlorosilane-based material that is in a liquid state under normal temperature and normal pressure, or a chlorosilane-based material that is in a gas state under normal temperature and normal pressure. In addition, the chlorosilane-based material refers to a silane-based material having a chloro group as a halogen group and refers to a source containing at least Si and Cl. The chlorosilane-based material referred to herein may be a kind of halide.

In this specification, the term “source” may refer to either or both of “a liquid source in a liquid state” and “a source gas in a gas state.” In this specification, the term “chlorosilane-based material” may refer to either or both of “a chlorosilane-based material in a liquid state” and “a chlorosilane-based source gas in a gas state.” When a liquid source that is in a liquid state under normal temperature and normal pressure such as HCDS is used, the liquid source is vaporized by a vaporization system such as a vaporizer and a bubbler and is supplied as a source gas (HCDS gas).

(Reaction Gas Supply System: Second Gas Supply System)

In thegas supply pipe42c, in order from an upstream end, anMFC44cand avalve46care provided, and the inertgas supply pipe52cis connected downstream from thevalve46c. In the inertgas supply pipe52c, in order from an upstream end, anMFC54cand avalve56care provided. Thenozzle40cis connected to a front end of thegas supply pipe42c.

Thenozzle40cis provided so as to extend upward in a stacking direction of thewafer24 from a bottom to a top of the inner wall of thereaction tube16. Thenozzle40cis provided so as to follow a region that is a side of a wafer arrangement region in which thewafer24 is arranged and that horizontally surrounds the wafer arrangement region. Thenozzle40cis configured as an L-shaped long nozzle. Thenozzle40cis provided such that a horizontal portion thereof penetrates a sidewall of the manifold18 and a vertical portion thereof extends upward from at least one end side of the wafer arrangement region toward the other end side.

Agas supply hole48cconfigured to supply a gas is provided in a side surface of thenozzle40c. Thegas supply hole48cfaces a center of thereaction tube16 and is configured to supply a gas toward thewafer24 accommodated in theprocess chamber22.

A plurality of gas supply holes48care provided from a bottom to a top of thereaction tube16.

Thegas supply pipe42dis connected downstream from thevalve46cof thegas supply pipe42cand thevalve56cof the inertgas supply pipe52c. In thegas supply pipe42d, in order from an upstream end, anMFC44dand avalve46dare provided, and the inertgas supply pipe52dis connected downstream from thevalve46d. In the inertgas supply pipe52d, in order from an upstream end, anMFC54dand avalve56dare provided.

The secondgas supply system34 mainly includes thenozzle40c, thegas supply pipes42cand42d, the MFCs44cand44d, and thevalves46cand46d. The inert gas supply system mainly includes the inertgas supply pipes52cand52d, the MFCs54cand54d, and thevalves56cand56d. The inert gas supply system also functions as a purge gas supply system.

A gas (oxygen-containing gas) which contains oxygen, that is an oxidizing gas (oxidation gas), is supplied from thegas supply pipe42cas a reaction gas. As an oxygen-containing gas, for example, oxygen (O₂) gas is supplied into theprocess chamber22 through theMFC44c, thevalve46c, thegas supply pipe42c, and thenozzle40c. At this time, the inert gas may also be supplied from the inertgas supply pipe52cinto thegas supply pipe42cthrough theMFC54cand thevalve56c.

A gas (hydrogen-containing gas) which contains hydrogen, that is a reducing gas (reduction gas), is supplied from thegas supply pipe42das a reaction gas. As a hydrogen-containing gas, for example, hydrogen (H₂) gas is supplied into theprocess chamber22 through theMFC44d, thevalve46d, thegas supply pipe42d, and thenozzle40c. At this time, an inert gas may also be supplied from the inertgas supply pipe52dinto thegas supply pipe42dthrough theMFC54dand thevalve56d.

In the present embodiment, the secondgas supply system34 functions as a reaction gas supply system.

(Cleaning Gas Supply System: Third Gas Supply System)

The cleaninggas supply pipe62ais connected to thegas supply pipe42c. In the cleaninggas supply pipe62a, in order from an upstream end, anMFC64aand avalve66aare provided. Thenozzle40cis connected to a front end of the cleaninggas supply pipe62athrough thegas supply pipe42c. In the cleaninggas supply pipe62b, in order from an upstream end, anMFC64band avalve66bare provided, and the inertgas supply pipe52bis connected downstream from thevalve66b. In the inertgas supply pipe52b, in order from an upstream end, anMFC54band avalve56bare provided. Thenozzle40bis connected to a front end of the cleaninggas supply pipe62b. Thenozzle40bis disposed so as to face an exhaust pipe90 (described later) with theboat28 accommodated in a process chamber20, that is, thewafer24, interposed therebetween as seen in a plan view (refer toFIG. 3). Also, inFIG. 1, positions of thenozzles40a,40b, and40c, theexhaust pipe90, and the like are conveniently shown for illustration.

Thenozzle40bis configured as an L-shaped short nozzle. Thenozzle40bis provided such that a horizontal portion thereof penetrates a sidewall of the manifold18 and a vertical portion thereof extends upward along an inner wall of the manifold18.

Agas supply hole48bconfigured to supply a gas is provided in a leading end of thenozzle40b, and thegas supply hole48bis opened upward [opened in a direction from the manifold18 side toward thereaction tube16 side]. Thenozzle40bis configured to supply a gas to the manifold18 side relative to a position in which thenozzle40asupplies a gas. In addition, thenozzle40bis able to supply a gas toward an inner wall surface of the manifold18.

A first cleaning gas supply system mainly includes thenozzle40c, the cleaninggas supply pipe62a, theMFC64a, and thevalve66a. In addition, a second cleaning gas supply system mainly includes thenozzle40b, the cleaninggas supply pipe62b, theMFC64b, and thevalve66b. Also, the inert gas supply system includes the inertgas supply pipe52b, theMFC54b, and thevalve56b. The inert gas supply system also functions as a purge gas supply system. The thirdgas supply system36 is a cleaning gas supply system that includes the first cleaning gas supply system and the second cleaning gas supply system.

In the present embodiment, a cleaning gas is supplied from the cleaninggas supply pipe62a. As the cleaning gas, for example, hydrogen fluoride (HF) gas is supplied as a gas containing fluorine (fluorine-containing gas) from the cleaninggas supply pipe62ainto the process chamber22 [mainly to the inner wall of the reaction tube16] through theMFC64a, thevalve66a, thegas supply pipe42c, and thenozzle40c. At this time, the inert gas may also be supplied from the inertgas supply pipes52cand52dinto theprocess chamber22 through the MFCs54cand54d, thevalves56cand56d, thegas supply pipe42c, and thenozzle40c.

Similarly, the cleaning gas is supplied from the cleaninggas supply pipe62b. As the cleaning gas, for example, hydrogen fluoride (HF) gas is supplied as a gas containing fluorine (fluorine-containing gas) from the cleaninggas supply pipe62binto the process chamber22 [mainly to an inner wall of the manifold18] through theMFC64b, thevalve66b, and thenozzle40b. At this time, the inert gas may also be supplied from the inertgas supply pipe52binto the cleaninggas supply pipe62bthrough theMFC54band thevalve56b.

In the present embodiment, the thirdgas supply system36 functions as a cleaning gas supply system.

In the present embodiment, a gas is transferred through thenozzle40aand thenozzle40cwhich are disposed in a toric longitudinal space formed by the inner wall of thereaction tube16 and ends of a plurality of stackedwafers24, that is, a cylindrical-shaped space. Through thegas supply hole48aand thegas supply hole48c, a gas is supplied into thereaction tube16 in the vicinity of thewafer24. A gas flow in thereaction tube16 is mainly in a direction (horizontal direction) parallel to a surface of thewafer24. Thereby, a gas is uniformly supplied to each of thewafers24 accommodated in theprocess chamber22 and a thin film having a uniform film thickness is formed on thewafer24. A gas (a residual gas after reaction) flowing over a surface of thewafer24 flows in a direction of theexhaust pipe90. The direction in which the residual gas flows is not limited to a vertical direction but may be appropriately set according to a position of an exhaust port.

(Exhaust System)

In thereaction tube16, theexhaust pipe90 configured to exhaust an atmosphere in theprocess chamber22 is provided. In theexhaust pipe90, avacuum pump96 is connected as a vacuum exhaust device through apressure sensor92 configured to detect a pressure in theprocess chamber22 as a pressure detector (pressure detecting unit) and an auto pressure controller (APC)valve94 serving as a pressure regulator (pressure regulating unit). While thevacuum pump96 is operated, vacuum-exhaust or vacuum-exhaust stop in theprocess chamber22 is performed by opening or closing theAPC valve94. In addition, while thevacuum pump96 is operated, a pressure in theprocess chamber22 is adjusted by regulating a degree of valve opening of the APC valve.

An exhaust system mainly includes theexhaust pipe90, thepressure sensor92, and theAPC valve94. Thevacuum pump96 may also be included in the exhaust system. While thevacuum pump96 is operated, the exhaust system regulates a degree of opening of theAPC valve94 based on information on the pressure detected by thepressure sensor92, and thereby vacuum-exhausts such that the pressure in theprocess chamber22 becomes a predetermined pressure (degree of vacuum). Theexhaust pipe90 is not limited to being provided in thereaction tube16 but may also be provided in the manifold18 similar to thenozzle40aor thenozzle40b.

(Opening and Closing Mechanism and Raising and Lowering Mechanism)

As a first furnace port cover, aseal cap100 configured to hermitically close a lower-end opening of the manifold18 is provided below themanifold18. Theseal cap100 is configured to abut a lower end of the manifold18 from a bottom side in a vertical direction. Theseal cap100 is made of a metal such as stainless and is formed in a disk shape. In a top surface of theseal cap100, as a seal member, anO ring20babutting the lower end of the manifold18 is provided.

In a side (a bottom side inFIG. 1) opposite to theprocess chamber22 of theseal cap100, arotating mechanism102 configured to rotate theboat28 is provided. Arotary shaft104 of therotating mechanism102 is made of a metal such as stainless and is connected to theboat28 by penetrating theseal cap100. Therotating mechanism102 rotates thewafer24 held on theboat28 by rotating theboat28.

Aboat elevator106 as a raising and lowering mechanism is vertically provided outside thereaction tube16. Theboat elevator106 is configured to raise and lower theseal cap100 in a vertical direction. Theboat elevator106 loads or unloads theboat28 mounted on theseal cap100 into or from theprocess chamber22 by raising or lowering theseal cap100. Theboat elevator106 functions as a transfer device (transfer mechanism) configured to transfer the boat28 [and thewafer24 held thereon] inside or outside theprocess chamber22.

As a second furnace port cover, ashutter110 configured to hermetically close a lower-end opening of the manifold18 is provided below themanifold18. Theshutter110 is formed in a disk shape and is made of a metal such as stainless. In a top surface of theshutter110, as a seal member, anO ring20cabutting the lower end of the manifold18 is provided. Theshutter110 closes the lower-end opening when theseal cap100 moves down and the lower-end opening of the manifold18 is opened, and is retracted from the lower-end opening when theseal cap100 moves up and the lower-end opening of the manifold18 is closed. Theshutter110 is controlled such that an opening and closing operation (such as a raising and lowering operation and a rotational operation) is performed by a shutter opening andclosing mechanism112 provided outside thereaction tube16.

In thereaction tube16, atemperature sensor114 serving as a temperature detector is provided (refer toFIG. 3). Power supply to theheater14 is adjusted based on information on the temperature detected by thetemperature sensor114, and thereby a temperature in theprocess chamber22 has a desired temperature distribution. Thetemperature sensor114 is configured as an L-shape similar to thenozzle40aand thenozzle40cand is provided along the inner wall of thereaction tube16.

Acontroller200 serving as a control unit (control device) is configured as a computer which includes a central processing unit (CPU)202, a random access memory (RAM)204, amemory device206, and an I/O port208. TheRAM204, thememory device206 and the I/O port208 are configured to exchange data with theCPU202 through aninternal bus210. An I/O device212 such as a touch panel is connected to thecontroller200.

Thememory device206 includes, for example, a flash memory and a hard disk drive (HDD). A control program controlling operations of asubstrate processing apparatus10, a process recipe describing sequences, conditions, and the like of substrate processing (film-forming process) (described later), a cleaning recipe describing sequences, conditions, and the like of a cleaning process (described later), and the like are readably stored in thememory device206.

The process recipe, which is a combination of sequences, causes thecontroller200 to execute each sequence in a substrate processing process in order to obtain a predetermined result, and functions as a program. Also, the cleaning recipe, which is a combination of sequences, causes thecontroller200 to execute each sequence in a cleaning process (described later) in order to obtain a predetermined result, and functions as a program. Hereinafter, the process recipe, the cleaning recipe, the control program, and the like are collectively simply called a “program.” In this specification, the term “program” may refer to only the process recipe, only the cleaning recipe, or only the control program, and any combination of the process recipe, the cleaning recipe and the control program.

TheRAM204 is configured as a memory area (work area) in which a program, data, and the like read by theCPU202 are temporarily stored.

The I/O port208 is connected to theMFCs44a,44c,44d,54a,54b,54c,54d,64a, and64b, thevalves46a,46c,46d,56a,56b,56c,56d,66a, and66b, thepressure sensor92, theAPC valve94, thevacuum pump96, theheater14, thetemperature sensor114, therotating mechanism102, theboat elevator106, the shutter opening andclosing mechanism112, and the like.

TheCPU202 reads and executes the control program from thememory device206, and reads the process recipe or the cleaning recipe from thememory device206 according to an input of a manipulating command from the I/O device212 and the like. To comply with content of the read process recipe or cleaning recipe, theCPU202 is configured to control a flow rate adjustment operation of various types of gases by theMFCs44a,44c,44d,54a,54b,54c,54d,64a, and64b, an opening and closing operation of thevalves46a,46c,46d,56a,56b,56c,56d,66a, and66b, a pressure adjustment operation by theAPC valve94 based on an opening and closing operation of theAPC valve94 and thepressure sensor92, starting and stopping of thevacuum pump96, a rotation and rotational speed regulating operation of theboat28 by therotating mechanism102, a raising and lowering operation of theboat28 by theboat elevator106, an opening and closing operation of theshutter110 by the shutter opening andclosing mechanism112, and the like.

Thecontroller200 is not limited to being configured as a dedicated computer but may be configured as a general-purpose computer. For example, anexternal memory device220 storing the program is prepared, the program is installed in the general-purpose computer using theexternal memory device220, and thereby thecontroller200 according to the present embodiment may also be configured. Examples of theexternal memory device220 may include a magnetic tape, a magnetic disk such as a flexible disk and a hard disk, an optical disc such as a CD and a DVD, a magneto-optical disc such as an MO, and a semiconductor memory such as a USB memory and a memory card.

A device for providing the program to the computer is not limited to theexternal memory device220 for providing the program. For example, the program may also be provided using a communication unit such as the Internet or a dedicated line without theexternal memory device220.

Thememory device206 or theexternal memory device220 is configured as a non-transitory computer-readable recording medium. Hereinafter, these are also collectively simply called a recording medium. When the term “recording medium” is used in this specification, it refers to either or both of thememory device206 and theexternal memory device220.

(2) Substrate Processing Process

Next, as a process of a manufacturing process of a semiconductor device using theprocessing furnace12 of thesubstrate processing apparatus10, a method in which a process of forming a thin film on thewafer24 as a substrate is performed, and then cleaning the inside of theprocess chamber22 is performed will be described. Operations of respective units constituting thesubstrate processing apparatus10 are controlled by thecontroller200.

When the term “wafer” is used in this specification, it refers to the “wafer itself,” or a “laminate (aggregate) of a wafer, a predetermined layer, film, and the like formed on a surface thereof” (that is, the wafer refers to a wafer including a predetermined layer, film, and the like formed on a surface thereof). In addition, when the term “surface of the wafer” is used in this specification, it refers to a “surface (exposed surface) of the wafer itself” or a “surface of a predetermined layer, film, and the like formed on the wafer, that is, the outermost surface of the wafer as the laminate.”

Therefore, when it is described in this specification that “a predetermined gas is supplied to the wafer,” it means that “a predetermined gas is directly supplied to a surface (exposed surface) of wafer itself” or “a predetermined gas is supplied to a layer, film, and the like formed on the wafer, that is, to the outermost surface of the wafer as the laminate.” In addition, when it is described in this specification that “a predetermined layer (or film) is formed on the wafer,” it means that “a predetermined layer (or film) is directly formed on a surface (exposed surface) of wafer itself” or “a predetermined layer (or film) is formed on a layer, film, and the like formed on the wafer, that is, form a predetermined layer (or film) on the outermost surface of the wafer as the laminate.”

The terms “substrate” and “wafer” as used in this specification have the same meanings. Thus, the term “wafer” in the above description may be replaced with the term “substrate.”

Hereinafter, an example in which a silicon oxide film (SiO₂film, hereinafter also referred to as a “SiO film”) is formed on thewafer24 using HCDS gas as a source gas and O₂gas and H₂gas as a reaction gas, and then the inside of theprocess chamber22 is cleaned using HF gas as a cleaning gas will be described with reference toFIGS. 5,6, and7.

<Wafer Charging and Boat Loading>

First, a plurality ofwafers24 are loaded on the boat28 (wafer charging). When thewafers24 are loaded on theboat28, theshutter110 is moved by the shutter opening andclosing mechanism112, and thereby the lower-end opening of the manifold18 is opened (shutter opening). Theboat28 on which the plurality ofwafers24 are held is lifted by theboat elevator106 and is loaded (boat loading) in theprocess chamber22. Theseal cap100 seals the lower end of the manifold18 through theO ring20b.

<Pressure Adjustment and Temperature Adjustment>

Subsequently, the inside of theprocess chamber22 is vacuum-exhausted to a desired pressure (degree of vacuum) by thevacuum pump96. At this time, the pressure in theprocess chamber22 is measured by thepressure sensor92, and theAPC valve94 is feedback-controlled (pressure adjustment) based on information on the measured pressure. Thevacuum pump96 constantly operates while at least processing on thewafer24 is completed.

The inside of theprocess chamber22 is heated to a desired temperature by theheater14. At this time, based on information on the temperature detected by thetemperature sensor114, power supply to theheater14 is feedback-controlled (temperature adjustment) such that the inside of theprocess chamber22 has a desired temperature distribution. Heating the inside of theprocess chamber22 by theheater14 is continuously preformed while at least processing on thewafer24 is completed.

Subsequently, theboat28 and thewafer24 are rotated by therotating mechanism102. Rotation of theboat28 and thewafer24 by therotating mechanism102 is continuously preformed while at least processing on thewafer24 is completed.

<Process of Forming Silicon Oxide Film>

Then, as illustrated inFIGS. 5 and 6, a SiO film having a predetermined film thickness is formed on thewafer24 by performing a cycle including the followingsteps1 to4 a predetermined number of times.

(Step1)

Instep1, a source gas (HCDS gas) is supplied to thewafer24 accommodated in the process chamber20 and a layer (silicon-containing layer) is formed on thewafer24.

First, thevalve46aof thegas supply pipe42ais opened, and the HCDS gas flows into thegas supply pipe42a. The HCDS gas flows from thegas supply pipe42aand a flow rate thereof is adjusted by theMFC44a. The HCDS having the adjusted flow rate is supplied from thegas supply hole48aof thenozzle40atoward thewafer24 in theprocess chamber22 in a heated and depressurized state and is exhausted from theexhaust pipe90. In this manner, the HCDS gas is supplied to the wafer24 (HCDS gas supply).

At this time, thevalve56aof the inertgas supply pipe52ais opened, and N₂gas may also be supplied as an inert gas from the inertgas supply pipe52a. A flow rate of the N₂gas is adjusted by theMFC54aand the N₂gas is supplied into thegas supply pipe42a. The N₂gas having the adjusted flow rate and the HCDS gas having the adjusted flow rate are mixed in thegas supply pipe42a, are supplied from thegas supply hole48aof thenozzle40ainto theprocess chamber22 in a heated and depressurized state, and are exhausted from theexhaust pipe90.

In order to prevent the HCDS gas from being introduced into thenozzles40band40c, thevalves56b,56c, and56dare opened, and the N₂gas flows into the inertgas supply pipes52b,52c, and52d. The N₂gas is supplied into theprocess chamber22 through the cleaninggas supply pipe62b, thegas supply pipe42c, thegas supply pipe42d, thenozzle40band thenozzle40c, and is exhausted from theexhaust pipe90.

At this time, theAPC valve94 is adjusted such that the pressure in theprocess chamber22 falls within, for example, a range of 1 Pa to 13,300 Pa, and preferably 10 Pa to 1,330 Pa. A supply flow rate of the HCDS gas controlled by theMFC44ais set to have a flow rate of, for example, a range of 1 sccm to 1,000 sccm. A supply flow rate of the N₂gas controlled by theMFCs54a,54b,54c, and54dis set to fall within, for example, a range of 100 sccm to 2,000 sccm. A time for supplying the HCDS gas to thewafer24, that is, a gas supply time (radiation time), is set to fall within, for example, the range of 1 second to 120 seconds.

The temperature of theheater14 is set such that the temperature of thewafer24 falls within, for example, a range of 350° C. to 800° C., preferably 450° C. to 800° C., and more preferably 550° C. to 750° C.

When the temperature of thewafer24 is less than 350° C., the HCDS is hardly decomposed and adsorbed on thewafer24, and thereby a practical film-forming rate may not be obtained. When the temperature of thewafer24 is set to 350° C. or more, this problem is addressed and thereby a sufficient film-forming rate may be obtained. When the temperature of thewafer24 is set to 450° C. or more, an effect of oxidizing power improvement is significant in step3 (described later). When the temperature of thewafer24 is set to 550° C. or more, the HCDS is sufficiently decomposed.

When the temperature of thewafer24 is set to 750° C., and particularly, more than 800° C., a CVD reaction becomes strong [a gas-phase reaction is dominant] so that film thickness uniformity is likely to be degraded and thereby control thereof may be difficult. When the temperature of thewafer24 is set to 800° C. or less, degradation of the film thickness uniformity is suppressed and thereby control thereof becomes easier. In particular, when the temperature of thewafer24 is set to 750° C. or less, the film thickness uniformity is easily secured and thereby control thereof becomes easy.

Under the above-described conditions, when the HCDS gas is supplied to thewafer24, a silicon-containing layer (Si-containing layer) having a thickness of, for example, about less than one atomic layer to several atomic layers is formed on the wafer24 [an underlying film of a surface]. The Si-containing layer may include either or both of a silicon layer (Si layer) and an adsorption layer of the HCDS gas. Preferably, the Si-containing layer is a layer containing silicon (Si) and chlorine (Cl).

The Si layer generically refers to a continuous layer formed of Si, a discontinuous layer, or a Si thin film formed by overlapping these layers. The continuous layer formed of Si may also be called a Si thin film. Si forming the Si layer also includes Si in which a bond with Cl is not completely disconnected.

The adsorption layer of the HCDS gas includes a chemical adsorption layer in which gas molecules of the HCDS gas are continuous and a chemical adsorption layer in which gas molecules of the HCDS gas are discontinuous. That is, the adsorption layer of the HCDS gas includes a chemical adsorption layer that is formed of the HCDS molecules and has a thickness of one molecule layer or less than one molecule layer. The HCDS (Si₂Cl₆) molecules forming the adsorption layer of the HCDS gas also include molecules in which a bond between Si and Cl is partially disconnected.

“Layer having a thickness of less than one atomic layer” refers to a discontinuously formed atomic layer. “Layer having a thickness of one atomic layer” refers to a continuously formed atomic layer. “Layer having a thickness of less than one molecule layer” refers to a discontinuously formed molecule layer. “Layer having a thickness of one molecule layer” refers to a continuously formed molecule layer.

Under conditions in which the HCDS gas is self-decomposed (pyrolyzed), that is, conditions causing a pyrolysis reaction of the HCDS, when Si is deposited on thewafer24, the Si layer is formed. Under conditions in which the HCDS gas is not self-decomposed (pyrolyzed), that is, conditions that do not cause a pyrolysis reaction of the HCDS, when the HCDS gas is adsorbed on thewafer24, the adsorption layer of the HCDS gas is formed. Forming the Si layer on thewafer24 is preferable since a film-forming rate is higher when the Si layer is formed on thewafer24 than when the adsorption layer of the HCDS gas is formed on thewafer24,

When the thickness of the Si-containing layer formed on thewafer24 is more than several atomic layers, an oxidation (modification) action instep3 does not influence on the entire Si-containing layer. Also, a minimum thickness of the Si-containing layer that can be formed on thewafer24 is less than one atomic layer. Therefore, preferably, the Si-containing layer may be set to have a thickness of less than one atomic layer to several atomic layers.

When the thickness of the Si-containing layer is set to one atomic layer or less, that is, one atomic layer or less than one atomic layer, an action of an oxidation reaction (modifying reaction) instep3 relatively increases, and a time required for the oxidation reaction instep3 decreases. Also, a time required for forming the Si-containing layer instep1 decreases. Thereby, a processing time required for performing one cycle decreases, and a processing time in total decreases. That is, the film-forming rate increases. In addition, when the thickness of the Si-containing layer is set to one atomic layer or less, controllability of the film thickness uniformity increases.

The HCDS gas supplied into theprocess chamber22 is supplied to thewafer24 and is also supplied to a surface of a member in the process chamber22 [a surface of a member such as the inner wall of thereaction tube16, the inner wall of the manifold18, and theboat28 provided in the process chamber22]. Thereby, the Si-containing layer is formed on thewafer24 and is also formed on the surface of the member in theprocess chamber22. The Si-containing layer formed on the surface of the member in theprocess chamber22 may also include either or both of a silicon layer (Si layer) and an adsorption layer of the HCDS gas as in the Si-containing layer formed on thewafer24.

As the source gas (a gas containing silicon and chlorine), instead of the HCDS gas, tetrachlorosilane (silicon tetrachloride, SiCl₄, abbreviated to STC) gas, trichlorosilane (SiHCl₃, abbreviated to TCS) gas, dichlorosilane (SiH₂Cl₂, abbreviated to DCS) gas, and monochlorosilane (SiH₃Cl, abbreviated to MCS) gas may also be used. As the inert gas, instead of the N₂gas, a rare gas such as argon (Ar), helium (He), neon (Ne), and xenon (Xe) may also be used.

(Step2)

After the Si-containing layer is formed on thewafer24, thevalve46aof thegas supply pipe42ais closed to suspend supply of the HCDS gas. While theAPC valve94 of theexhaust pipe90 is opened, the inside of theprocess chamber22 is vacuum-exhausted by thevacuum pump96, and a residual gas (an unreacted HCDS gas and/or an HCDS gas that has contributed to formation of the Si-containing layer) in theprocess chamber22 is removed from the inside of the process chamber22 (residual gas removal).

While thevalves56a,56b,56c, and56dare opened, supply of the N₂gas into theprocess chamber22 continues. The N₂gas serves as a purge gas and an effect of removing the residual gas in theprocess chamber22 from the inside of theprocess chamber22 increases. The HCDS gas adsorbed on the member in theprocess chamber22 instep1 is not completely removed by vacuum-exhausting the inside of theprocess chamber22, and at least some gas remains while being adsorbed on the surface of the member in theprocess chamber22.

In this case, the residual gas in theprocess chamber22 may not be completely removed and the inside of theprocess chamber22 may not be completely purged. When an amount of the residual gas in theprocess chamber22 is small, there is no substantial influence instep3 performed thereafter. There is no need to set a flow rate of the N₂gas supplied into theprocess chamber22 to be high. For example, when the same amount of the N₂gas as a volume of the process container [the process chamber22] is supplied, it is possible to purge to the extent that there is no substantial influence instep3. When the inside of theprocess chamber22 is not completely purged in this way (the next process begins at a step at which the gases have been purged to some extent), a purge time decreases, thereby improving the throughput. Also, it is possible to suppress unnecessary consumption of the N₂gas to the minimum.

Similar to the temperature of thewafer24 when the HCDS gas is supplied, the temperature of theheater14 is set to fall within, for example, a range of 350° C. to 800° C., preferably 450° C. to 800° C., and more preferably 550° C. to 750° C. The supply flow rate of the N₂gas supplied from each inert gas supply system as a purge gas is set to have a flow rate of, for example, a range of 100 sccm to 2,000 sccm. As the purge gas, instead of the N₂gas, a rare gas such as Ar, He, Ne, and Xe may also be used.

(Step3)

Instep3, as a reaction gas, the O₂gas and the H₂gas are supplied to theheated wafer24 in the process chamber20 under sub-atmospheric pressure. The layer (Si-containing layer) formed instep1 is oxidized and modified to an oxide layer.

After the residual gas in theprocess chamber22 is removed, thevalve46cof thegas supply pipe42cis opened and the O₂gas flows into thegas supply pipe42c. The O₂gas flows from thegas supply pipe42cand a flow rate thereof is adjusted by theMFC44c. The O₂gas having the adjusted flow rate is supplied from thegas supply hole48cof thenozzle40cinto theprocess chamber22 in a heated and depressurized state.

Thevalve46dof thegas supply pipe42dis opened and the H₂gas flows into thegas supply pipe42d. The H₂gas flows from thegas supply pipe42dand a flow rate thereof is adjusted by theMFC44d. The H₂gas having the adjusted flow rate is supplied from thegas supply hole48cof thenozzle40cinto theprocess chamber22 in a heated and depressurized state through thegas supply pipe42c.

When the H₂gas passes through thegas supply pipe42c, the H₂gas is mixed with the O₂gas in thegas supply pipe42c. The mixed gas of the O₂gas and the H₂gas is supplied from thegas supply hole48cof thenozzle40cto thewafer24 in theprocess chamber22 in a heated and depressurized state, and then is exhausted from theexhaust pipe90. In this manner, the O₂gas and the H₂gas are supplied to the wafer24 (O₂gas+H₂gas supply).

At this time, thevalve56cof the inertgas supply pipe52cis opened and the N₂gas may also be supplied from the inertgas supply pipe52c. A flow rate of the N₂gas is adjusted by theMFC54cand the N₂gas is supplied into thegas supply pipe42c. Also, thevalve56dof the inertgas supply pipe52dis opened and the N₂gas may also be supplied as an inert gas from the inertgas supply pipe52d. A flow rate of the N₂gas is adjusted by theMFC54dand the N₂gas is supplied into thegas supply pipe42c. In this case, a mixed gas of the O₂gas, the H₂gas and the N₂gas is supplied from thenozzle40c. As the inert gas, instead of the N₂gas, a rare gas such as Ar, He, Ne, and Xe may also be used.

In order to prevent the O₂gas and H₂gas from being introduced into thenozzles40aand40b, thevalves56aand56bare opened, and the N₂gas flows into the inertgas supply pipes52aand52b. The N₂gas is supplied into theprocess chamber22 through thegas supply pipe42aand thenozzle40a, the cleaninggas supply pipe62band thenozzle40b, and is exhausted from theexhaust pipe90.

By adjusting theAPC valve94, the pressure in theprocess chamber22 is maintained below atmospheric pressure, for example, in a range of 1 Pa to 1,000 Pa. The supply flow rate of the O₂gas controlled by theMFC44cis set to have a flow rate of, for example, a range of 1,000 sccm to 10,000 sccm. The supply flow rate of the H₂gas controlled by theMFC44dis set to have a flow rate of, for example, a range of 1,000 sccm to 10,000 sccm. The supply flow rate of the N₂gas controlled by theMFCs54a,54b,54c, and54dis set to have a flow rate of, for example, a range of 100 sccm to 2,000 sccm. A time for supplying the O₂gas and the H₂gas to thewafer24, that is, a gas supply time [radiation time] is set to fall within, for example, a range of 1 second to 120 seconds.

Similar to the temperature range of thewafer24 when the HCDS gas is supplied instep1, the temperature of theheater14 is set to have the temperature range in which oxidizing power is significantly improved (described later), for example, a range of 450° C. to 800° C., and preferably 550° C. to 750° C. When the temperature falls within this range, oxidizing power significantly increases by adding the H₂gas to the O₂gas under a depressurized atmosphere. In addition, when the temperature of thewafer24 is excessively low, it is difficult to increase the oxidizing power.

In consideration of the throughput, it is preferable that the temperature of theheater14 be set to maintain the temperature in theprocess chamber22 fromsteps1 to3 to the same temperature range. It is preferable that the temperature of theheater14 be set to maintain the temperature in theprocess chamber22 fromsteps1 to4 to the same temperature range. In this case, the temperature of theheater14 is set such that the temperature in theprocess chamber22 is maintained constant to fall within, for example, a range of 450° C. to 800° C., and preferably 550° C. to 750° C., fromsteps1 to4.

Under the above-described conditions, when the O₂gas and the H₂gas are supplied into theprocess chamber22, the O₂gas and the H₂gas are thermally activated (excited) as non-plasma and reacted under a heated and depressurized atmosphere. Thereby, a water (H₂O)-free oxidizing species which contains oxygen such as atomic oxygen (O) is generated. Then, the oxidation reaction is mainly performed on the Si-containing layer formed on thewafer24 instep1 by this oxidizing species. Since energy of the oxidizing species is higher than bond energy of Si—N, Si—Cl, Si—H, and Si—C included in the Si-containing layer, when the energy of the oxidizing species is applied to the Si-containing layer, bonds of Si—N, Si—Cl, Si—H, and Si—C included in the Si-containing layer are disconnected. N, H, Cl, and C, whose bonds with Si are disconnected, are removed from the film and discharged as N₂, H₂, Cl₂, HCl, CO₂, and the like. Also, when bonds with N, H, Cl, and C are disconnected, the remaining bonds of Si combine with O included in the oxidizing species and Si—O bonds are formed. In this way, the Si-containing layer is changed to a silicon oxide layer (SiO₂layer, hereinafter referred to simply as a SiO layer) having low content of impurities such as Cl (modified).

According to the oxidation reaction, it is possible to significantly increase the oxidizing power compared to when only the O₂gas is supplied or water vapor (H₂O) is supplied. Under a depressurized atmosphere, when the H₂gas is added with the O₂gas, it is possible to significantly increase the oxidizing power compared to when only the O₂gas is supplied or the H₂O gas is supplied.

The oxidizing species generated in theprocess chamber22 is supplied to thewafer24 and is also supplied to the surface of the member in theprocess chamber22. As a result, a part of the Si-containing layer formed on the surface of the member in theprocess chamber22 is changed to a SiO layer similar to the Si-containing layer formed on the wafer24 (modified).

Instep3, either or both of the O₂gas and the H₂gas may flow by being activated as plasma. When the O₂gas and/or the H₂gas flow by being activated as plasma, the oxidizing species including an active species having higher energy may be generated. When the oxidation reaction is performed using this oxidizing species, device characteristics may also improve.

In the above-described temperature range, when the O₂gas and the H₂gas are activated by heat and sufficiently reacted, an H₂O-free oxidizing species such as atomic oxygen (O) is sufficiently generated. Thereby, when the O₂gas and the H₂gas are thermally activated as non-plasma, it is possible to obtain sufficient oxidizing power. When the O₂gas and the H₂gas are supplied by being activated by heat, there is no plasma damage and a relatively soft reaction can be generated. Therefore, it is possible to perform the above-described oxidation reaction relatively softly.

As the oxygen-containing gas, that is, the oxidizing gas, instead of the O₂gas, ozone (O₃) gas and the like may also be used. In the above-described temperature range, a test was performed to observe an effect of adding the hydrogen-containing gas to nitric oxide (NO) gas or nitrous oxide (N₂O) gas. The result showed that an effect of oxidizing power improvement is not obtained compared to when only the NO gas or the N₂O gas is supplied. As the oxygen-containing gas, an N-free oxygen-containing gas (a gas containing O without N) is preferably used.

As the hydrogen-containing gas, that is, the reducing gas, instead of the H₂gas, deuterium (D₂) gas and the like may also be used. When ammonia (NH₃) gas, methane (CH₄) gas, and the like are used, nitrogen (N) impurities or carbon (C) impurities may be considered to be mixed into the film. As the hydrogen-containing gas, an other-element-free hydrogen-containing gas (a gas containing hydrogen or deuterium without any other elements) is preferably used.

As the oxygen-containing gas, at least one gas selected from the group consisting of the O₂gas and the O₃gas may be used. As the hydrogen-containing gas, at least one gas selected from the group consisting of the H₂gas and the D₂gas may be used.

(Step4)

After the Si-containing layer is changed to the SiO oxide layer, thevalve46cof thegas supply pipe42cis closed to suspend supply of the O₂gas. Also, thevalve46dof thegas supply pipe42dis closed to suspend supply of the H₂gas. While theAPC valve94 of theexhaust pipe90 is opened, the inside of theprocess chamber22 is vacuum-exhausted by thevacuum pump96, and the remaining O₂gas and H₂gas, the reaction by-products, and the like are removed from the inside of the process chamber22 (removal of residual gas). While thevalves56a,56b,56c, and56dare opened, supply of the N₂gas as an inert gas into theprocess chamber22 is maintained. The N₂gas serves as a purge gas and further increases an effect of removing the unreacted gas or O₂gas that has contributed to formation of the SiO layer, the H₂gas, the reaction by-products, and the like remaining in theprocess chamber22 from the inside theprocess chamber22.

At this time, the residual gas in theprocess chamber22 may not be completely removed and the inside of theprocess chamber22 may not be completely purged. When an amount of the residual gas in theprocess chamber22 is small, there is no substantial influence instep1 performed thereafter. There is no need to set a flow rate of the N₂gas supplied into theprocess chamber22 to be high. For example, when the same amount of the N₂gas as a volume of the reaction tube16 [the process chamber22] is supplied, it is possible to purge to the extent that there is no substantial influence instep1. When the inside of theprocess chamber22 is not completely purged in this way (the next process begins at a step at which the gases are purged to some extent), a purge time decreases, thereby improving the throughput. Also, it is possible to suppress unnecessary consumption of the N₂gas to the minimum.

Similar to the temperature of thewafer24 when the O₂gas and the H₂gas are supplied, the temperature of theheater14 is set to fall within, for example, a range of 450° C. to 800° C., and preferably 550° C. to 750° C. The supply flow rate of the N₂gas supplied as a purge gas from each inert gas supply system is set to have a flow rate of, for example, a range of 100 sccm to 2,000 sccm. As the purge gas, instead of the N₂gas, a rare gas such as Ar, He, Ne, and Xe may also be used.

<Performing Predetermined Number of Times>

When acycle including steps1 to4 is performed a predetermined number of times (n times), a SiO film having a predetermined film thickness is formed on thewafer24.

<Purging and Restoring to Atmospheric Pressure>

After the SiO film having a predetermined film thickness is formed, thevalves56a,56b,56c, and56dare opened, and the N₂gas is supplied as an inert gas from each of the inertgas supply pipes52a,52b,52c, and52dinto theprocess chamber22 and is exhausted from theexhaust pipe90. The N₂gas serves as a purge gas, the inside of theprocess chamber22 is purged with the inert gas, and the residual gas in theprocess chamber22 is removed from the inside of the process chamber22 (purge). Then, the atmosphere in theprocess chamber22 is replaced with the inert gas, and the pressure in theprocess chamber22 is restored to the normal pressure (restoration to atmospheric pressure).

<Boat Unloading and Wafer Discharge>

Theseal cap100 is lowered by theboat elevator106, and thereby the lower end of the manifold18 is opened, and the processedwafer24 is unloaded (boat unloading) to the outside of thereaction tube16 from the lower end of the manifold18 while being held on theboat28. After the boat is unloaded, theshutter110 moves by the shutter opening andclosing mechanism112 and the lower-end opening of the manifold18 is sealed by theshutter110 through theO ring20c(shutter closing). Then, the processedwafer24, that is, the batch-processedwafer24, is extracted from the boat28 (wafer discharge).

<Cleaning Process>

Subsequently, cleaning of the inside of theprocess chamber22 is performed. During the process of forming the SiO film, a film is also deposited on inner walls of thereaction tube16 and the manifold18, the surface of theboat28, and the like. This deposited film (deposition film) is accumulated and becomes gradually thicker when the above-described batch process is repeatedly performed. This accumulated deposition film is released therefrom in a subsequent process and is adhered to thewafer24, thereby becoming a foreign material. For this reason, in preparation for the subsequent process, the deposition film is removed from the inside of theprocess chamber22 when the deposition film has a predetermined thickness.

(Boat Loading)

The boat28 [empty boat28] having nowafer24 loaded thereon is loaded in theprocess chamber22 according to the same sequences as in the above-described boat loading.

(Pressure Adjustment and Temperature Adjustment)

The inside of theprocess chamber22 is vacuum-exhausted to a desired pressure (degree of vacuum) by thevacuum pump96. At this time, the pressure in theprocess chamber22 is measured by thepressure sensor92, and theAPC valve94 is feedback-controlled based on information on the measured pressure (pressure adjustment). Thevacuum pump96 constantly operates while at least cleaning of the inside of theprocess chamber22 is completed.

The inside of theprocess chamber22 is heated to a desired temperature by theheater14. At this time, based on information on the temperature detected by thetemperature sensor114, power supply to theheater14 is feedback-controlled (temperature adjustment) such that the inside of theprocess chamber22 has a desired temperature distribution. Heating the inside of theprocess chamber22 by theheater14 is continuously preformed while at least cleaning of the inside of theprocess chamber22 is completed.

Subsequently, theboat28 is rotated by therotating mechanism102. Rotation of theboat28 by therotating mechanism102 is continuously performed while at least cleaning of the inside of theprocess chamber22 is completed. Also, theboat28 may not be rotated.

Cleaning Gas SupplyExample 1

Subsequently, a cleaning gas is supplied into theprocess chamber22. In Example 1 of a cleaning gas supply pattern, as illustrated inFIG. 7, first, the cleaning gas is supplied from thenozzle40cand then the cleaning gas is supplied from thenozzle40b.

Since thenozzle40cis used to supply the reaction gas for modifying the Si-containing layer formed on thewafer24, it is configured to supply the gas to the vicinity of thewafer24 accommodated in theprocess chamber22. Thereby, thenozzle40cis more likely to supply the gas to thereaction tube16 side, that is a part (top inFIG. 1) in which thewafer24 in theprocess chamber22 is accommodated, than the manifold18 side. Therefore, when the gas is supplied from thenozzle40c, thereaction tube16 side is more likely to be cleaned than the manifold18 side. On the other hand, thenozzle40bis configured to supply the gas to the manifold18 side rather than thenozzle40c. Thereby, thenozzle40bis more likely to supply the gas to the manifold18 side, for example, the inner wall surface of the manifold18, than thereaction tube16 side. As a result, when the gas is supplied from thenozzle40b, the manifold18 side is more likely to be cleaned than thereaction tube16 side.

Also, the HCDS gas supplied into theprocess chamber22 instep1 is supplied to thewafer24 and is also supplied to the surface of the member in the process chamber. In addition, the oxidizing species generated in theprocess chamber22 instep3 is supplied to thewafer24 and is also supplied to the surface of the member in theprocess chamber22. As a result, a part of the Si-containing layer formed on the surface of the member in theprocess chamber22 instep1 is changed (modified) to the SiO layer similar to the Si-containing layer formed on thewafer24 instep3. However, instep3, a supply amount of the H₂O-free oxidizing species containing oxygen such as atomic oxygen (O) becomes smaller in the low-temperature region [a region that is not surrounded by theheater14 and is a region other than a region horizontally surrounding the wafer arrangement region] in theprocess chamber22 than the high-temperature region [a region that is surrounded by theheater14 and is a region horizontally surrounding the wafer arrangement region]. In addition, instep1, the adsorption layer of the HCDS gas is likely to be formed thicker in the low-temperature region of theprocess chamber22 than the high-temperature region. As a result, the Si-containing layer formed on the low-temperature region is unreacted or partially reacted, and is likely to remain in an insufficient oxidation state. Specifically, the adsorption layer of the HCDS gas formed on a lower part of the inner wall of thereaction tube16, the inner wall of the manifold18, lower parts of thenozzles40aand40c, the top surface of theseal cap100, a side surface of therotary shaft104, a side surface or a bottom surface of theinsulation member30, the inner wall of theexhaust pipe90, and the like out of the members in theprocess chamber22 is unreacted or partially reacted, and is likely to remain in an insufficient oxidation state.

In addition, when the boat unloading is performed, outside air [atmosphere] containing H₂O is introduced from the lower-end opening of the manifold18 into theprocess chamber22. Thereby, the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, the side surface or the bottom surface of theinsulation member30, and the like are exposed to the atmosphere containing H₂O. As described above, the thick adsorption layer of the HCDS gas is formed on the lower part of the inner wall of thereaction tube16, the inner wall of the manifold18, the lower parts of thenozzles40aand40c, the top surface of theseal cap100, the side surface of therotary shaft104, the side surface or the bottom surface of theinsulation member30, the inner wall of theexhaust pipe90, and the like out of the members in theprocess chamber22, and remains in an insufficient oxidation state. When the boat unloading is performed in this state, the adsorption layer of the HCDS gas may be oxidized by the H₂O in the atmosphere and changed to reaction by-products containing Cl. Also, a film (deposition film) formed by deposition of the reaction by-products is relatively fragile and easily released therefrom, thereby easily becoming a foreign material (particles).

For this reason, when the cleaning gas is supplied from a side closer to the manifold18 toward the low-temperature region, even if the deposition film, which is relatively fragile and easily released therefrom, is formed on the low-temperature region, this deposition film is easily cleaned and the deposition film is effectively removed from the inside of the process chamber20.

In this manner, when the cleaning gas is supplied from thenozzle40cand thenozzle40b, a time required for cleaning the inside of theprocess chamber22 is reduced compared to when only thenozzle40cis used to supply the cleaning gas (Comparative Example 1 inFIG. 7).

In the process of supplying the cleaning gas, specifically, thevalve66aof the cleaninggas supply pipe62ais opened and the HF gas flows into the cleaninggas supply pipe62a. The HF gas flows from the cleaninggas supply pipe62aand a flow rate thereof is adjusted by theMFC64a. The HF gas having the adjusted flow rate is supplied from thegas supply hole48cof thenozzle40cinto theprocess chamber22, comes in contact with the inner walls of thereaction tube16 and the manifold18, the surface of theboat28, and the like, and is exhausted from theexhaust pipe90. At this time, thevalve56bof the inertgas supply pipe52bis opened and the N₂gas is supplied as an inert gas from thenozzle40b. By the HF gas supplied from thenozzle40cand the N₂gas supplied from thenozzle40b, as illustrated inFIG. 8a, cleaning is mainly performed on a region having a relatively high temperature such as the inner wall of thereaction tube16, the surface of theboat28, and the like (high-temperature region cleaning).

Also, at this time, in order to prevent the HF gas from being introduced into thenozzle40a, it is preferable that thevalve56abe opened and the N₂gas flow into the inertgas supply pipe52a. In this case, the N₂gas is supplied into theprocess chamber22 through thegas supply pipe42aand thenozzle40aand is exhausted from theexhaust pipe90.

After the HF gas is supplied from thenozzle40cfor a predetermined time, thevalve66aof the cleaninggas supply pipe62aand thevalve56bof the inertgas supply pipe52bare closed to suspend supply of the HF gas from the cleaninggas supply pipe62aand supply of the N₂gas from the inertgas supply pipe52b. Subsequently, thevalve66bof the cleaninggas supply pipe62bis opened and the HF gas flows into the cleaninggas supply pipe62b. The HF gas flows from the cleaninggas supply pipe62band a flow rate thereof is adjusted by theMFC64b. The HF gas having the adjusted flow rate is supplied from thegas supply hole48bof thenozzle40binto theprocess chamber22, comes in contact with the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like, and is exhausted from theexhaust pipe90. At this time, thevalves56cand56dof the inertgas supply pipes52cand52dare opened, and the N₂gas is supplied as an inert gas from thenozzle40c. By the HF gas supplied from thenozzle40band the N₂gas supplied from thenozzle40c, as illustrated inFIG. 8b, cleaning is mainly performed on a region having a relatively low temperature such as the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like (low-temperature region cleaning). After the HF gas is supplied from thenozzle40bfor a predetermined time, thevalve66bof the cleaninggas supply pipe62band thevalves56cand56dof the inertgas supply pipes52cand52dare closed to suspend supply of the HF gas from the cleaninggas supply pipe62band supply of the N₂gas from the inertgas supply pipes52cand52d.

Also, at this time, in order to prevent the HF gas from being introduced into thenozzle40a, it is preferable that thevalve56abe opened and the N₂gas flow into the inertgas supply pipe52a. In this case, the N₂gas is supplied into theprocess chamber22 through thegas supply pipe42aand thenozzle40aand is exhausted from theexhaust pipe90.

When cleaning is performed, theAPC valve94 is adjusted such that the pressure in theprocess chamber22 is set to fall within, for example, a range of 133 Pa to 50,000 Pa. The supply flow rate of the HF gas controlled by theMFCs64aand64bis set to have a flow rate of, for example, a range of 1 sccm to 1,000 sccm. The temperature of theheater14 is preferably set such that the temperature of theprocess chamber22 falls within, for example, a range of 75° C. or more and less than 100° C. When the HF gas is used as the cleaning gas and the temperature is less than 75° C., the HF gas may be adsorbed in multiple layers on the surfaces of thereaction tube16, the manifold18, and the like. This multilayer adsorption may cause a corrosion reaction. In addition, when the temperature is 100° C. or more, the metal member may be corroded.

Instead of using only the HF gas as the cleaning gas, a gas in which the HF gas is diluted with an inert gas such as N₂gas, Ar gas, and He gas, a mixed gas of the HF gas and fluorine (F₂) gas, a mixed gas of the HF gas and chlorine fluoride (ClF₃) gas, ClF₃gas, and the like may also be used.

<Purging and Restoring to Atmospheric Pressure>

After the HF gas is supplied for a predetermined time and the deposition film is removed, thevalves56a,56b,56c, and56dare opened, the N₂gas is supplied as an inert gas from each of the inertgas supply pipes52a,52b,52c, and52dinto theprocess chamber22, and is exhausted from theexhaust pipe90. The N₂gas serves as a purge gas, the inside of theprocess chamber22 is purged with the inert gas, and the residual gas in theprocess chamber22 is removed from the inside of the process chamber22 (purge). Then, the atmosphere in theprocess chamber22 is replaced with the inert gas, and the pressure in theprocess chamber22 is restored to the normal pressure (restoration to atmospheric pressure).

<Boat Unloading>

According to the same sequences as in the above-described boat unloading, theboat28 is unloaded to the outside of thereaction tube16. Then, the lower-end opening of the manifold18 is sealed by theshutter110.

Similar to the above-described Example 1, when the high-temperature region cleaning and the low-temperature region cleaning are non-simultaneously performed, that is, asynchronously performed, while the inert gas such as the N₂gas is supplied into thereaction tube16 through thenozzle40awhen cleaning is performed on the low-temperature region, the HF gas is preferably supplied to the inner wall surface of the manifold18 through thenozzle40b. At this time, more preferably, the inert gas such as the N₂gas is supplied into thereaction tube16 through thenozzle40c.

In this way, by the N₂gas supplied into thereaction tube16, the HF gas supplied toward the inner wall surface of the manifold18 through thenozzle40bmay be pushed downward. That is, by the N₂gas supplied into thereaction tube16, it is possible to suppress (block) the HF gas supplied toward the inner wall surface of the manifold18 through thenozzle40bfrom flowing and diffusing into an upper part in thereaction tube16. Thereby, the HF gas supplied through thenozzle40bmay aggressively (intensively) come in contact with the low-temperature region such as the inner wall surface of the manifold18, and it is possible to efficiently remove the deposition that is adhered to the low-temperature region such as the inner wall surface of the manifold18 and is relatively difficult to remove. It is confirmed that removing the deposition adhered to the low-temperature region such as the inner wall surface of the manifold18 is more difficult than removing the deposition adhered to the high-temperature region such as the inner wall surface of thereaction tube16. According to regulation of flowing and diffusing of the HF gas by the N₂gas, it is possible to efficiently remove the deposition that is adhered to the low-temperature region and is relatively difficult to remove.

In addition, unlike the low-temperature region cleaning, the HF gas is preferably supplied into thereaction tube16 through thenozzle40cwhile the inert gas such as the N₂gas is supplied into the manifold18 through thenozzle40bwhen cleaning is performed on the high-temperature region. Thereby, the HF gas supplied into thereaction tube16 is pressured up from the bottom, and it is possible to suppress (block) the HF gas from flowing and diffusing into themanifold18. Accordingly, it is possible to efficiently remove the deposition adhered to the inner wall of thereaction tube16.

Also, it is preferable that a supply concentration [a concentration of the HF gas in thenozzle40b] of the HF gas supplied through thenozzle40bwhen cleaning is performed on the low-temperature region be set higher than a supply concentration [a concentration of the HF gas in thenozzle40c] of the HF gas supplied through thenozzle40cwhen cleaning is performed on the high-temperature region. For example, the supply concentration of the HF gas supplied through thenozzle40bis set to 80% to 100%, for example, 100%, and the supply concentration of the HF gas supplied through thenozzle40cis set to 10% to 30%, for example, 10% to 20%. Thereby, by the high-concentration HF gas supplied through thenozzle40b, it is possible to efficiently remove the deposition that is adhered to the low-temperature region such as the inner wall surface of the manifold18 and is relatively difficult to remove. As described above, it is confirmed that removing the deposition adhered to the low-temperature region such as the inner wall surface of the manifold18 is more difficult than removing the deposition adhered to the high-temperature region such as the inner wall surface of thereaction tube16. By adjusting the concentration of the HF gas, it is possible to efficiently remove the deposition that is adhered to the low-temperature region and is relatively difficult to remove. Also, the supply concentration of the HF gas may be represented by, for example, an equation “supply flow rate of HF gas/(supply flow rate of HF gas+supply flow rate of N₂gas)”, and each supply concentration of HF gas may be controlled by, for example, adjusting the supply flow rate of the HF gas and the supply flow rate of the N₂gas supplied into each nozzle. For example, the supply concentration of the HF gas supplied through thenozzle40bmay be controlled by adjusting the supply flow rate of the HF gas supplied into the cleaninggas supply pipe62band the supply flow rate of the N₂gas supplied into the inertgas supply pipe52bby the MFCs64band54b, respectively. Also, for example, the supply concentration of the HF gas supplied through thenozzle40cmay be controlled by adjusting the supply flow rate of the HF gas supplied into the cleaninggas supply pipe62aand the supply flow rate of the N₂gas supplied into the inertgas supply pipes52cand52dby theMFCs64a,54c, and54d, respectively.

As a gas supply pattern when the cleaning gas is supplied, the following Examples 2 to 5 may also be used instead of the above-described Example 1.

Cleaning Gas SupplyExample 2

In Example 2 of a cleaning gas supply pattern, the cleaning gas is supplied from thenozzle40cand the cleaning gas is also supplied from thenozzle40b.

Specifically, thevalve66aof the cleaninggas supply pipe62ais opened and the HF gas flows into the cleaninggas supply pipe62a. The HF gas flows from the cleaninggas supply pipe62aand a flow rate thereof is adjusted by theMFC64a. The HF gas having the adjusted flow rate is supplied from thegas supply hole48cof thenozzle40cinto theprocess chamber22, comes in contact with the inner walls of thereaction tube16 and the manifold18, the surface of theboat28, and the like, and is exhausted from theexhaust pipe90. Cleaning is mainly performed on a region having a relatively high temperature such as the inner wall of thereaction tube16 and the surface of theboat28 by the HF gas supplied from thenozzle40c.

At the same time, thevalve66bof the cleaninggas supply pipe62bis opened and the HF gas flows into the cleaninggas supply pipe62b. The HF gas flows from the cleaninggas supply pipe62band a flow rate thereof is adjusted by theMFC64b. The HF gas having the adjusted flow rate is supplied from thegas supply hole48bof thenozzle40binto theprocess chamber22, comes in contact with the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like, and is exhausted from theexhaust pipe90. Cleaning is mainly performed on a region having a relatively low temperature such as the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like by the HF gas supplied from thenozzle40b. After the HF gas is supplied from thenozzle40cand thenozzle40bfor a predetermined time, thevalve66aof the cleaninggas supply pipe62aand thevalve66bof the cleaninggas supply pipe62bare closed to suspend supply of the HF gas from the cleaninggas supply pipe62aand the cleaninggas supply pipe62b.

Also, at this time, in order to prevent the HF gas from being introduced into thenozzle40a, it is preferable that thevalve56abe opened and the N₂gas flow into the inertgas supply pipe52a. In this case, the N₂gas is supplied into theprocess chamber22 through thegas supply pipe42aand thenozzle40aand is exhausted from theexhaust pipe90.

According to Example 2, a time required for cleaning is reduced compared to that of Comparative Example 1 and is further reduced compared to that of Example 1.

Cleaning Gas SupplyExample 3

In Example 3 of a cleaning gas supply pattern, supply of the cleaning gas from thenozzle40cand supply of the cleaning gas from thenozzle40bare alternately performed a plurality of times.

Specifically, thevalve66aof the cleaninggas supply pipe62ais opened and the HF gas flows into the cleaninggas supply pipe62a. The HF gas flows from the cleaninggas supply pipe62aand a flow rate thereof is adjusted by theMFC64a. The HF gas having the adjusted flow rate is supplied from thegas supply hole48cof thenozzle40cinto theprocess chamber22, comes in contact with the inner walls of thereaction tube16 and the manifold18, the surface of theboat28, and the like, and is exhausted from theexhaust pipe90. At this time, thevalve56bof the inertgas supply pipe52bis opened and the N₂gas is supplied as an inert gas from thenozzle40b. By the HF gas supplied from thenozzle40cand the N₂gas supplied from thenozzle40b, as illustrated inFIG. 8a, cleaning is mainly performed on a region having a relatively high temperature such as the inner wall of thereaction tube16, the surface of theboat28, and the like (high-temperature region cleaning).

Also, at this time, in order to prevent the HF gas from being introduced into thenozzle40a, it is preferable that thevalve56abe opened and the N₂gas flow into the inertgas supply pipe52a. In this case, the N₂gas is supplied into theprocess chamber22 through thegas supply pipe42aand thenozzle40aand is exhausted from theexhaust pipe90.

After the HF gas is supplied from thenozzle40cfor a predetermined time (a time shorter than that of Example 1), thevalve66aof the cleaninggas supply pipe62aand thevalve56bof the inertgas supply pipe52bare closed to suspend supply of the HF gas from the cleaninggas supply pipe62aand supply of the N₂gas from the inertgas supply pipe52b. Subsequently, thevalve66bof the cleaninggas supply pipe62bis opened and the HF gas flows into the cleaninggas supply pipe62b. The HF gas flows from the cleaninggas supply pipe62band a flow rate thereof is adjusted by theMFC64b. The HF gas having the adjusted flow rate is supplied from thegas supply hole48bof thenozzle40binto theprocess chamber22, comes in contact with the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like, and is exhausted from theexhaust pipe90. At this time, thevalves56cand56dof the inertgas supply pipes52cand52dare opened, and the N₂gas is supplied as an inert gas from thenozzle40c. By the HF gas supplied from thenozzle40band the N₂gas supplied from thenozzle40c, as illustrated inFIG. 8b, cleaning is mainly performed on a region having a relatively low temperature such as the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like (low-temperature region cleaning). After the HF gas is supplied from thenozzle40bfor a predetermined time (a time shorter than that of Example 1), thevalve66bof the cleaninggas supply pipe62band thevalves56cand56dof the inertgas supply pipes52cand52dare closed to suspend supply of the HF gas from the cleaninggas supply pipe62band supply of the N₂gas from the inertgas supply pipes52cand52d.

Also, at this time, in order to prevent the HF gas from being introduced into thenozzle40a, it is preferable that thevalve56abe opened and the N₂gas flow into the inertgas supply pipe52a. In this case, the N₂gas is supplied into theprocess chamber22 through thegas supply pipe42aand thenozzle40aand is exhausted from theexhaust pipe90.

Supply of the HF gas from thenozzle40cand supply of the N₂gas from thenozzle40b, and supply of the HF gas from thenozzle40band supply of the N₂gas from thenozzle40care alternately performed a plurality of times. That is, the high-temperature region cleaning and the low-temperature region cleaning are alternately repeatedly performed.

According to Example 3, a time required for cleaning is reduced compared to that of Comparative Example 1 as much as in Example 1. Also, when the high-temperature region cleaning and the low-temperature region cleaning is set as one cycle, according to the number of times the cycle is performed, it is possible to control a removal amount (etching amount) of the deposition respectively adhered to the high-temperature region and the low-temperature region

Cleaning Gas SupplyExample 4

In Example 4 of a cleaning gas supply pattern, while the cleaning gas is continuously supplied from thenozzle40b, the cleaning gas is intermittently supplied from thenozzle40c.

Specifically, thevalve66bof the cleaninggas supply pipe62bis opened and the HF gas flows into the cleaninggas supply pipe62b. The HF gas flows from the cleaninggas supply pipe62band a flow rate thereof is adjusted by theMFC64b. The HF gas having the adjustedflow rate22 is supplied from thegas supply hole48bof thenozzle40binto theprocess chamber22, comes in contact with the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like, and is exhausted from theexhaust pipe90. Cleaning is mainly performed on a region having a relatively low temperature such as the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like by the HF gas supplied from thenozzle40b.

To this end, thevalve66aof the cleaninggas supply pipe62ais opened and the HF gas flows into the cleaninggas supply pipe62a. The HF gas flows from the cleaninggas supply pipe62aand a flow rate thereof is adjusted by theMFC64a. The HF gas having the adjusted flow rate is supplied from thegas supply hole48cof thenozzle40cinto theprocess chamber22, comes in contact with the inner walls of thereaction tube16 and the manifold18, the surface of theboat28, and the like, and is exhausted from theexhaust pipe90. Cleaning is mainly performed on a region having a relatively high temperature such as the inner wall of thereaction tube16, the surface of theboat28, and the like by the HF gas supplied from thenozzle40c. After the HF gas is supplied from thenozzle40cfor a predetermined time (a time shorter than that of Example 1), thevalve66aof the cleaninggas supply pipe62ais closed to suspend supply of the HF gas from the cleaninggas supply pipe62a. Subsequently, after a predetermined time [for example, a time for which thevalve66ais opened] passes, thevalve66aof the cleaninggas supply pipe62ais opened again, and the HF gas flows into the cleaninggas supply pipe62a. By repeating this manipulation, the HF gas is intermittently supplied from thenozzle40c.

According to Example 4, a time required for cleaning is reduced compared to that of Comparative Example 1 and is further reduced compared to that of Example 1. Also, since a time for contacting the HF gas with the region having a relatively low temperature may be set to be greater than a time for contacting the HF gas with the region having a relatively high temperature, it is possible to intensively perform cleaning on the region having a relatively low temperature.

Cleaning Gas SupplyExample 5

In Example 5 of a cleaning gas supply pattern, while the cleaning gas is continuously supplied from thenozzle40c, the cleaning gas is intermittently supplied from thenozzle40b.

Specifically, thevalve66aof the cleaninggas supply pipe62ais opened and the HF gas flows into the cleaninggas supply pipe62a. The HF gas flows from the cleaninggas supply pipe62aand a flow rate thereof is adjusted by theMFC64a. The HF gas having the adjusted flow rate is supplied from thegas supply hole48cof thenozzle40cinto theprocess chamber22, comes in contact with the inner walls of thereaction tube16 and the manifold18, the surface of theboat28, and the like, and is exhausted from theexhaust pipe90. Cleaning is mainly performed on a region having a relatively high temperature such as the inner wall of thereaction tube16 and the surface of theboat28 by the HF gas supplied from thenozzle40c.

To this end, thevalve66bof the cleaninggas supply pipe62bis opened and the HF gas flows into the cleaninggas supply pipe62b. The HF gas flows from the cleaninggas supply pipe62band a flow rate thereof is adjusted by theMFC64b. The HF gas having the adjustedflow rate22 is supplied from thegas supply hole48bof thenozzle40binto theprocess chamber22, comes in contact with the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like, and is exhausted from theexhaust pipe90. Cleaning is mainly performed on a region having a relatively low temperature such as the inner wall of the manifold18, the top surface of theseal cap100, the side surface of therotary shaft104, and the like by the HF gas supplied from thenozzle40b. After the HF gas is supplied from thenozzle40bfor a predetermined time (a time shorter than that of Example 1), thevalve66bof the cleaninggas supply pipe62bis closed to suspend supply of the HF gas from the cleaninggas supply pipe62b. Subsequently, after a predetermined time [for example, a time for which thevalve66bis opened] passes, thevalve66bof the cleaninggas supply pipe62bis opened again, and the HF gas flows into the cleaninggas supply pipe62b. By repeating this manipulation, the HF gas is intermittently supplied from thenozzle40b.

According to Example 5, a time required for cleaning is reduced compared to that of Comparative Example 1, is further reduced compared to that of Example 1, and is equally reduced as in Example 4.

Second Embodiment

Next, the second embodiment will be described. In the first embodiment, the L-shapednozzle40bincluding thegas supply hole48bopened upward is connected to the cleaninggas supply pipe62b. In the second embodiment, thenozzle320bis connected to the cleaninggas supply pipe62b. This is a difference between the two embodiments. In the present embodiment, the same numerals are assigned to substantially the same components as those in the first embodiment and descriptions thereof will not be repeated.

As illustrated inFIG. 9, thenozzle320bhas an I shape [short pipe shape], and a main body portion is provided to penetrate a sidewall of the manifold18 such that a leading end thereof is substantially flush with the inner wall of the manifold18. Also, the leading end of thenozzle320bmay be projected from the inner wall of the manifold18.

Agas supply hole322bconfigured to supply a gas is provided in the leading end of thenozzle320b. Thegas supply hole322bis configured to be opened [opened to a direction from the inner wall side of the manifold18 to the inner side] toward a side (horizontal direction). Thenozzle320bis configured to supply a gas to the inner side in the process chamber20 from the manifold18 side relative to a position in which thenozzle40asupplies a gas. In addition, thenozzle320bis able to supply a gas to the inner wall surface of the manifold18.

Third Embodiment

Next, the third embodiment will be described. In the first embodiment, thenozzle40bincluding thegas supply hole48bopened upward is connected to the cleaninggas supply pipe62b. In the third embodiment, anozzle330bis connected to the cleaninggas supply pipe62b. This is a difference between the two embodiments. In the present embodiment, the same numerals are assigned to substantially the same components as those in the first embodiment and descriptions thereof will not be repeated.

As illustrated inFIG. 10, thenozzle330bis an L-shaped short nozzle, and is provided such that a horizontal portion thereof penetrates a sidewall of the manifold18 and a vertical portion thereof extends upward along an inner wall of the manifold18.

Agas supply hole332bis provided in the sidewall of the manifold18 side of the vertical portion of thenozzle330b, and thegas supply hole332bis configured to be opened toward the inner wall surface of the manifold18. That is, thegas supply hole332bis provided so as to face (oppose) the inner wall surface of the manifold18. Thenozzle330bis configured to directly supply a gas from the manifold18 side to the inner wall side of the manifold18 relative to a position in which thenozzle40asupplies a gas.

Fourth Embodiment

Next, the fourth embodiment will be described. In the first embodiment, thenozzle40bincluding thegas supply hole48bopened upward is connected to the cleaninggas supply pipe62b. In the fourth embodiment, anozzle340bis connected to the cleaninggas supply pipe62b. This is a difference between the two embodiments. In the present embodiment, the same numerals are assigned to substantially the same components as those in the first embodiment and descriptions thereof will not be repeated.

As illustrated inFIG. 11, thenozzle340bis an L-shaped short nozzle, and is provided such that a horizontal portion thereof penetrates a sidewall of the manifold18 and a vertical portion thereof extends upward along an inner wall of the manifold18.

Agas supply hole342bconfigured to supply a gas is provided in a leading end of thenozzle340b, and thegas supply hole342bis opened upward [opened in a direction from the manifold18 side to thereaction tube16 side]. Also, agas supply hole344bis provided in a sidewall of the manifold18 side of the vertical portion of thenozzle340b. Thegas supply hole344bis configured to be opened toward the inner wall surface of the manifold18. Thenozzle340bis configured to supply a gas to the upper part in the process chamber20 and the inner wall side of the manifold18 from the manifold18 side relative to a position in which thenozzle40asupplies a gas. Thenozzle340bis able to directly supply a gas toward the inner wall surface of the manifold18.

Fifth Embodiment

Next, the fifth embodiment will be described. In the first embodiment, thenozzle40bincluding thegas supply hole48bopened upward is connected to the cleaninggas supply pipe62b. In the fifth embodiment, anozzle350bis connected to the cleaninggas supply pipe62b. This is a difference between the two embodiments. In the present embodiment, the same numerals are assigned to substantially the same components as those in the first embodiment and descriptions thereof will not be repeated.

As illustrated inFIG. 12, thenozzle350bis an L-shaped short nozzle, and is provided such that a horizontal portion thereof penetrates a sidewall of the manifold18 and a vertical portion thereof extends downward along an inner wall of the manifold18.

Agas supply hole352bconfigured to supply a gas is provided in a leading end of thenozzle350b, and thegas supply hole352bis opened downward [opened in a direction from the manifold18 side to theseal cap100 side]. That is, thegas supply hole352bis provided so as to face (oppose) theseal cap100. Thenozzle350bis configured to supply a gas to the lower part in the process chamber20 from the manifold18 side relative to a position in which thenozzle40asupplies a gas. Thenozzle350bis able to directly supply a gas toward the top surface of theseal cap100.

Sixth Embodiment

Next, the sixth embodiment will be described. In the first embodiment, thenozzle40bincluding thegas supply hole48bopened upward is connected to the cleaninggas supply pipe62b. In the sixth embodiment, anozzle360bis connected to the cleaninggas supply pipe62b. This is a difference between the two embodiments. In the present embodiment, the same numerals are assigned to substantially the same components as those in the first embodiment and descriptions thereof will not be repeated.

As illustrated inFIG. 13, thenozzle360bis an L-shaped short nozzle, and is provided such that a horizontal portion thereof penetrates a sidewall of the manifold18 and a vertical portion thereof extends downward along an inner wall of the manifold18.

Agas supply hole362bconfigured to supply a gas is provided in a leading end of thenozzle360b, and thegas supply hole362bis opened downward [opened in a direction from the manifold18 side to theseal cap100 side]. That is, thegas supply hole362bis provided so as to face (oppose) theseal cap100. Also, agas supply hole364bis provided in a sidewall of the manifold18 side of the vertical portion of thenozzle360b. Thegas supply hole364bis configured to be opened toward the inner wall surface of the manifold18. That is, thegas supply hole364bis provided so as to face (oppose) themanifold18. Thenozzle360bis configured to supply a gas to the lower part in the process chamber20 and the inner wall side of the manifold18 from the manifold18 side relative to a position in which thenozzle40asupplies a gas. Thenozzle360bis able to directly supply a gas toward the top surface of theseal cap100 and the inner wall surface of the manifold.

Seventh Embodiment

Next, the seventh embodiment will be described. In the seventh embodiment, acover400 covering the inner wall surface is provided in the inner wall surface of the manifold18 side of the first embodiment. As illustrated inFIG. 14, thecover400 is provided on the top surface of theseal cap100, and made of, for example, a heat-resistant material (nonmetallic material) such as quartz and SiC. Thegas supply hole48bof thenozzle40bis disposed in a gap between thecover400 and the manifold18, and the HF gas flows between thecover400 and the manifold18.

It is preferable that thecover400 be provided concentrically with the manifold18 in the inner side of the manifold18. That is, it is preferable that thecover400 be provided to cover the entire inner wall surface of the manifold18 so as to face (oppose) the inner wall surface of the manifold18. In such a configuration, since the HF gas comes in contact with the inner wall surface of the manifold18 more aggressively (intensively), it is possible to efficiently remove the deposition that is adhered to the inner wall surface of the manifold18 and is relatively difficult to remove. Thecover400 serves as a guide portion, which allows the HF gas to aggressively flow along the inner wall surface of the manifold18, that is, a gas flow regulating portion (gas flow regulating unit).

Eighth Embodiment

Next, the eighth embodiment will be described. In the eighth embodiment, similar to the seventh embodiment, acover410 covering the inner wall surface is provided in the inner wall side of themanifold18 of the first embodiment. As illustrated inFIG. 15, thecover410 includes atop surface portion410aand aside surface portion410b. Thetop surface portion410ais configured to horizontally extend from an upper end of theside surface portion410bto the outside [the manifold18 side]. Thetop surface portion410ais also called an extending portion. Since theside surface portion410bvertically extends [is suspended] from an end of thetop surface portion410ato a lower part, it is also called a suspended portion. Aprotrusion18ahorizontally projecting toward the inner side of the manifold18 is provided in an upper end of the inner wall of the manifold18. Thetop surface portion410aof thecover410 is supported by theprotrusion18a. Theprotrusion18aserves as a support portion supporting thecover410. Thecover410 is provided such that a lower part thereof is opened, and is made of, for example, a heat-resistant material (nonmetallic material) such as quartz and SiC. Thegas supply hole48bof thenozzle40bis disposed in a gap between thecover410 and the manifold18, and the HF gas flows between thecover410 and the manifold18.

It is preferable that thecover410 be provided concentrically with the manifold18 in the inner side of the manifold18. That is, it is preferable that thecover410 be provided to cover substantially the entire inner wall surface of the manifold18 so as to face (oppose) the inner wall surface of the manifold18. In such a configuration, since the HF gas comes in contact with the inner wall surface of the manifold18 more aggressively (intensively), it is possible to efficiently remove the deposition that is adhered to the inner wall surface of the manifold18 and is relatively difficult to remove. Thecover410 serves as a guide portion, which allows the HF gas to aggressively flow along the inner wall surface of the manifold18, that is, a gas flow regulating portion (gas flow regulating unit).

Even in such a configuration, since the HF gas comes in contact with the inner wall surface of the manifold18 more aggressively (intensively), it is possible to efficiently remove the deposition that is adhered to the inner wall surface of the manifold18 and is relatively difficult to remove.

Also, thetop surface portion410aof thecover410 may be provided between thereaction tube16 and the manifold18. In this case, since there is no need to provide theprotrusion18ain the manifold18, it is possible to simplify a shape of the manifold18, thereby reducing a processing cost of the manifold18, that is, a manufacturing cost of the substrate processing apparatus. In addition, the top surface of thecover410 may be opened by providing an opening such as a slit and a hole in thetop surface portion410aof thecover410 and the top surface of thecover410. Also, an upper part may be opened by reversing thecover410 upside down.

Also, thecovers400 and410 and each nozzle of the first to sixth embodiments may be appropriately combined.

In the above-described first to eighth embodiments, while a case in which thesubstrate processing apparatus10 having no plasma source has been described, the present invention is not limited thereto but the plasma source may be used. However, when the plasma source is not included, it is possible to simplify a structure of the substrate processing apparatus compared to when the plasma source is included. Therefore, it is possible to reduce a manufacturing cost of the substrate processing apparatus.

In the above embodiment, the HF gas is not supplied from thenozzle40a. While deposition having SiO as a main component is adhered to the member in the process chamber20 in the process of forming the SiO film, deposition having Si as a main component is adhered to the inside of thenozzle40a, that is, the inner wall of thenozzle40a, since only HCDS gas flows into thenozzle40a. However, it is difficult to remove the deposition having Si as a main component using the HF gas. Therefore, in the cleaning process, even when the HF gas flows into thenozzle40a, it is difficult to remove the deposition having Si as a main component adhered to the inner wall of thenozzle40a.

Also, when the HF gas flows into thenozzle40a, the HF gas may be introduced into a gap between the deposition having Si as a main component adhered to the inner wall of thenozzle40aand the inner wall of thenozzle40a. Thereby, an interface between the inner wall of thenozzle40aand the deposition having Si as a main component may become unstable. When the process of forming the SiO film is performed in this state, the deposition having Si as a main component adhered to the inner wall of thenozzle40ais partially released therefrom during the film-forming, and thereby a foreign material may be generated and adhered to thewafer24.

Therefore, in the present embodiment, the HF gas is not supplied into thereaction tube16 through thenozzle40ain the cleaning process and the HF gas is supplied into thereaction tube16 through thenozzle40c. That is, supply of the HF gas into thereaction tube16 through thenozzle40ais not performed.

When the HF gas is supplied into thereaction tube16 through thenozzle40c, in order to prevent the HF gas from being introduced into thenozzle40a, it is preferable that an inert gas such as the N₂gas be supplied into thenozzle40a. That is, it is preferable that thevalve56aof the inertgas supply pipe52abe opened and the N₂gas as an inert gas be supplied from the inertgas supply pipe52a. Thereby, it is possible to prevent the foreign material from being generated due to an unstable interface between the inner wall of thenozzle40aand the deposition having Si as a main component.

Also, there is no need to clean the inside of thenozzle40a, that is, to remove the deposition having Si as a main component adhered to the inner wall of thenozzle40a. Thenozzle40amay be exchanged when an accumulated film has a predetermined thickness of, for example, 4 μm to 5 μm, that is a thickness before the foreign material is generated after a release occurs in the deposition.

Also, in the present embodiment, even when the HF gas is supplied toward the inner wall surface of the manifold18 through thenozzle40b, the HF gas may not be supplied into thereaction tube16 through thenozzle40a.

Even when the HF gas is supplied toward the inner wall surface of the manifold18 through thenozzle40b, in order to prevent the HF gas from being introduced into thenozzle40a, it is preferable that an inert gas such as the N₂gas be supplied into thenozzle40a. Thereby, it is possible to prevent the foreign material from being generated due to an unstable interface between the inner wall of thenozzle40aand the deposition having Si as a main component. At this time, it is preferable that the HF gas be prevented from being introduced into thenozzle40cby supplying the inert gas such as the N₂gas into thenozzle40c.

In addition, in the process of forming the SiO film, since only the O₂gas or the H₂gas flows into thenozzle40c, no deposition is adhered to the inside of thenozzle40c, that is, the inner wall of thenozzle40c, or even when the deposition is adhered thereto, it is caused by a small amount of the HCDS gas introduced into thenozzle40c, and thereby only a small amount of the deposition is adhered thereto. As a result, there is no need to clean the inside of thenozzle40c.

Also, in the above embodiment, while a configuration in which the O₂gas and the H₂gas are supplied through the same nozzle [thenozzle40c] into theprocess chamber22 has been described, the present invention is not limited thereto and each gas may also be supplied into theprocess chamber22 from a separate nozzle. However, when a plurality of types of gases use a common nozzle, it is advantageous in that the number of nozzles decreases, a device cost decreases, and maintenance becomes easier, compared to when separate nozzles are provided. The nozzle for supplying the HCDS gas and the nozzle for supplying the H₂gas may share a nozzle and the gases may be supplied through the same nozzle. This is because, under the above-described processing conditions, when the H₂gas and the HCDS gas adhered to the inside of the nozzle come in contact, there is no film-forming reaction. In addition, it is preferable that the nozzle for supplying the HCDS gas and the nozzle for supplying the O₂gas be separately provided. This is because, according to temperature conditions, when the O₂gas and the HCDS gas adhered to the inside of the nozzle come in contact, the film-forming reaction is generated and the thick deposition may be formed.

In the above embodiment, while the example in which the chlorosilane-based source gas is used as a source gas when the Si-containing layer is formed instep1 has been described, instead of the chlorosilane-based source gas, a fluorosilane-based material gas or a silane-based material gas having a halogen-based ligand other than a chloro group may also be used.

The fluorosilane-based material gas refers to a fluorosilane-based material in a gas state, for example, a gas obtained by vaporizing a fluorosilane-based material that is in a liquid state under normal temperature and normal pressure, or a fluorosilane-based material that is in a gas state under normal temperature and normal pressure. In addition, the fluorosilane-based material refers to a silane-based material having a fluoro group as a halogen group, and a source including at least silicon (Si) and fluorine (F). That is, the fluorosilane-based material may also be a kind of halide.

As the fluorosilane-based material gas, a silicon fluoride gas such as tetrafluorosilane [silicon tetrafluoride (SiF₄)] gas and hexafluorodisilane (Si₂F₆) gas may be used. In this case, when the Si-containing layer is formed, the fluorosilane-based material gas is supplied to thewafer24 in theprocess chamber22. The Si-containing layer formed in this way includes either or both of the adsorption layer of the fluorosilane-based material gas and the Si layer.

In the above embodiment, while the example in which, instep3 of the process of forming the SiO film, the O₂gas and the H₂gas are supplied into theprocess chamber22 that is heated under sub-atmospheric pressure, and the Si-containing layer is changed to the SiO layer has been described, the present invention is not limited thereto. Instep3, the H₂gas is not supplied and only the oxygen-containing gas such as O₂gas, O₃gas, and H₂O gas may be supplied. In addition, these oxygen-containing gases may also be supplied by being activated as plasma.

In the above embodiment, while the example in which the HCDS gas, the O₂gas and the H₂gas are alternately supplied into theprocess chamber22 to from the SiO film on thewafer24 has been described, the present invention is not limited thereto. Alternatively, the HCDS gas and the oxygen-containing gas such as the O₂gas, the O₃gas, and the H₂O gas may be simultaneously supplied into theprocess chamber22 to form the SiO film on thewafer24.

In the above embodiment, while the example in which the silicon-based thin film including silicon, that is a semiconductor element, is formed as a thin film, has been described, the present invention is not limited thereto. The present invention may also be preferably applied when a metal-based thin film containing a metal element such as titanium (Ti), zirconium (Zr), hafnium (Hf), tantalum (Ta), aluminum (Al), and molybdenum (Mo) is formed as a thin film.

As a metal-based thin film containing Ti, when a titanium oxide film (TiO film) is formed, as a source gas, for example, a gas which contains Ti and a chloro group such as titanium tetrachloride (TiCl₄) or a gas which contains Ti and a fluoro group such as titanium tetrafluoride (TiF₄) may be used. As an oxygen-containing gas and a hydrogen-containing gas, the same gases as in the above-described embodiment may be used. Processing conditions may be the same, for example, as in the above-described embodiment.

As a metal-based thin film containing Zr, when a zirconium oxide film (ZrO film) is formed, as a source gas, for example, a gas which contains Zr and a chloro group such as zirconium tetrachloride (ZrCl₄) or a gas which contains Zr and a fluoro group such as zirconium tetrafluoride (ZrF₄) may be used. As an oxygen-containing gas and a hydrogen-containing gas, the same gases as in the above-described embodiment may be used. Processing conditions may be the same, for example, as in the above-described embodiment.

As a metal-based thin film containing Hf, when a hafnium oxide film (HfO film) is formed, as a source gas, for example, a gas which contains Hf and a chloro group such as hafnium tetrachloride (HfCl₄) or a gas which contains Hf and a fluoro group such as hafnium tetrafluoride (HfF₄) may be used. As an oxygen-containing gas and a hydrogen-containing gas, the same gases as in the above-described embodiment may be used. Processing conditions may be the same, for example, as in the above-described embodiment.

As a metal-based thin film containing Ta, when a tantalum oxide film (TaO film) is formed, as a source gas, for example, a gas which contains Ta and a chloro group such as tantalum pentachloride (TaCl₅) or a gas which contains Ta and a fluoro group such as tantalum pentafluoride (TaF₅) may be used. As an oxygen-containing gas and a hydrogen-containing gas, the same gases as in the above-described embodiment may be used. Processing conditions may be the same, for example, as in the above-described embodiment.

As a metal-based thin film containing Al, when an aluminum oxide film (AlO film) is formed, as a source gas, for example, a gas which contains Al and a chloro group such as aluminum trichloride (AlCl₃) or a gas which contains Al and a fluoro group such as aluminum trifluoride (AlF₃) may be used. As an oxygen-containing gas and a hydrogen-containing gas, the same gases as in the above-described embodiment may be used. Processing conditions may be the same, for example, as in the above-described embodiment.

As a metal-based thin film containing Mo, when a molybdenum oxide film (MoO film) is formed, as a source gas, for example, a gas which contains Mo and a chloro group such as molybdenum pentachloride (MoCl₅) or a gas which contains Mo and a fluoro group such as molybdenum pentafluoride (MoF₅) may be used. As an oxygen-containing gas and a hydrogen-containing gas, the same gases as in the above-described embodiment may be used. Processing conditions may be the same, for example, as in the above-described embodiment.

In this way, the present invention is applied to form the silicon-based thin film and is also applied to form the metal-based thin film. In this case, the same action effects as in the above-described embodiment may be obtained. That is, the present invention may be preferably applied when a thin film including a predetermined element such as a semiconductor element and a metal element is formed.

In the above embodiment, while the case in which, in the cleaning process, after the boat is loaded, the cleaning gas is supplied into the process chamber20 [cleaning the inside of the process chamber20 is performed while theboat28 is accommodated in the process chamber20] has been described, the present invention is not limited thereto. When cleaning of theboat28 is unnecessary, the boat loading may be skipped [while theboat28 is not accommodated in the process chamber20] and the cleaning gas may also be supplied into the process chamber20.

In the above embodiment, while the example in which a thin film is formed using the batch-type substrate processing apparatus that processes a plurality of substrates at once has been described, the present invention is not limited thereto but may also be preferably applied when a thin film is formed using a single wafer type substrate processing apparatus that processes a single substrate or several substrates at once.

In the above embodiment, while the example in which the substrate processing apparatus including a hot wall-type processing furnace is used to form a thin film has been described, the present invention is not limited thereto but may also be preferably applied to when a substrate processing apparatus including a cold wall-type processing furnace is used to form a thin film.

The first to eighth embodiments, each of Examples, and the like may be appropriately combined and used.

In any of the first to eighth embodiments, when Example 2 of a cleaning gas supply pattern is applied, in any embodiment, the process of supplying the cleaning gas into thereaction tube16 and the process of supplying the cleaning gas toward the inner wall surface of the manifold18 are simultaneously performed. In particular, in the third, fourth, and sixth to eighth embodiments, when Example 2 of a cleaning gas supply pattern is applied, the process of supplying the cleaning gas into thereaction tube16 and the process of directly supplying the cleaning gas toward the inner wall surface of the manifold18 or the top surface of theseal cap100 are simultaneously performed.

In any of the third, fourth, and sixth to eighth embodiments, when Example 3 of a cleaning gas supply pattern is applied, the process of supplying the cleaning gas into thereaction tube16 and the process of directly supplying the cleaning gas toward the inner wall surface of the manifold18 or the top surface of theseal cap100 are alternately repeatedly performed.

In any of the third, fourth, and sixth to eighth embodiments, when any of Examples 3 to 5 of a cleaning gas supply pattern is applied, at least one of the process of supplying the cleaning gas into thereaction tube16 and the process of directly supplying the cleaning gas toward the inner wall surface of the manifold18 or the top surface of theseal cap100 is intermittently performed.

In any of the third, fourth, and sixth to eighth embodiments, when Example 4 or 5 of a cleaning gas supply pattern is applied, either the process of supplying the cleaning gas into thereaction tube16 or the process of directly supplying the cleaning gas toward the inner wall surface of the manifold18 or the top surface of theseal cap100 is intermittently performed, and the other process is continuously performed.

The present invention may also be implemented by changing, for example, a process recipe or a cleaning recipe of a predetermined substrate processing apparatus. When the process recipe or the cleaning recipe is changed, the process recipe or the cleaning recipe according to the present invention is installed in the predetermined substrate processing apparatus through telecommunication lines or a recording medium storing the process recipe or the cleaning recipe, or the process recipe or the cleaning recipe is directly changed to a process recipe or a cleaning recipe according to the present invention by manipulating an input and output device of the predetermined substrate processing apparatus.

According to the present invention, it is possible to reduce a time required for cleaning.

Preferred Embodiments of the Present Invention

Hereinafter, preferred embodiments of the present invention are added.

(Supplementary Note 1)

According to an embodiment of the present invention, there is provided a cleaning method, including:

(a) providing a process chamber after forming an oxide film on a substrate in the process chamber formed by a reaction tube and a manifold supporting the reaction tube by performing a cycle a predetermined number of times, the cycle including supplying a source gas to the substrate in the process chamber through a first nozzle disposed in the manifold and extending upward from the manifold to an inside of the reaction tube, and supplying an oxidizing gas to the substrate in the process chamber through a second nozzle disposed in the manifold and extending upward from the manifold to the inside of the reaction tube; and

(b) cleaning an inside of the process chamber,

wherein the step (b) includes:

a first cleaning process of supplying a hydrogen fluoride gas into the reaction tube through the second nozzle; and

a second cleaning process of supplying a hydrogen fluoride gas onto an inner wall surface of the manifold through a third nozzle disposed in the manifold.

(Supplementary Note 2)

In the cleaning method ofSupplementary note 1, it is preferable that the first cleaning process and the second cleaning process are performed without supplying the hydrogen fluoride gas into the reaction tube through the first nozzle. That is, in the first cleaning process, the hydrogen fluoride gas is not supplied into the reaction tube through the first nozzle and the hydrogen fluoride gas is supplied into the reaction tube through the second nozzle. In the second cleaning process, the hydrogen fluoride gas is not supplied into the reaction tube through the first nozzle and the hydrogen fluoride gas is supplied toward the inner wall surface of the manifold through the third nozzle.

(Supplementary Note 3)

In the cleaning method ofSupplementary note 1 or 2, it is preferable that the first cleaning process and the second cleaning process are performed with an inert gas being supplied into the reaction tube through the first nozzle.

(Supplementary Note 4)

In the cleaning method of any ofSupplementary notes 1 to 3, it is preferable that a concentration of the hydrogen fluoride gas supplied through the third nozzle in the second cleaning process (a concentration of the hydrogen fluoride gas in the third nozzle) is higher than that of the hydrogen fluoride gas supplied through the second nozzle in the first cleaning process (a concentration of the hydrogen fluoride gas in the second nozzle).

(Supplementary Note 5)

In the cleaning method of any ofSupplementary notes 1 to 4, it is preferable that the first cleaning process and the second cleaning process are non-simultaneously performed (asynchronously performed).

(Supplementary Note 6)

In the cleaning method of any ofSupplementary notes 1 to 5, it is preferable that the first cleaning process and the second cleaning process are alternately performed.

(Supplementary Note 7)

In the cleaning method of any ofSupplementary notes 1 to 8, it is preferable that the first cleaning process and the second cleaning process are alternately repeated.

(Supplementary Note 8)

In the cleaning method of any ofSupplementary notes 5 to 7, it is preferable that the second cleaning process is performed with an inert gas being supplied into the reaction tube through the second nozzle.

(Supplementary Note 9)

In the cleaning method of any ofSupplementary notes 5 to 8, it is preferable that the second cleaning process is performed with an inert gas being supplied into the reaction tube through the first nozzle and the second nozzle.

(Supplementary Note 10)

In the cleaning method of Supplementary note 8 or 9, it is preferable that the hydrogen fluoride gas supplied onto the inner wall surface of the manifold through the third nozzle is pushed downward by the inert gas supplied into the reaction tube in the second cleaning process.

(Supplementary Note 11)

In the cleaning method of any of Supplementary notes 8 to 9, it is preferable that the hydrogen fluoride gas supplied onto the inner wall surface of the manifold through the third nozzle is prevented (blocked) from flowing and diffusing into an upper portion in the reaction tube (an upper portion within the reaction tube) by the inert gas supplied into the reaction tube in the second cleaning process.

(Supplementary Note 12)

In the cleaning method of any ofSupplementary notes 1 to 4, it is preferable that the first cleaning process and the second cleaning process are simultaneously performed.

(Supplementary Note 13)

In the cleaning method of any ofSupplementary notes 1 to 12, it is preferable that at least one of the first cleaning process and the second cleaning process is intermittently performed.

(Supplementary Note 14)

In the cleaning method of any ofSupplementary notes 1 to 13, it is preferable that a reducing gas is further supplied to the substrate in the process chamber under sub-atmospheric pressure through the first nozzle when supplying the oxidizing gas in the cycle.

(Supplementary Note 15)

In the cleaning method of any ofSupplementary notes 1 to 14, it is preferable that a layer is formed on the substrate in the process chamber by supplying the source gas to the substrate in the process chamber through the first nozzle when supplying the source gas in the cycle, and

the layer is oxidized and modified to an oxide layer by supplying the oxidizing gas to the substrate in the process chamber through the second nozzle and supplying a reducing gas through the first nozzle under sub-atmospheric pressure when supplying the oxidizing gas in the cycle.

(Supplementary Note 16)

According to another embodiment of the present invention, there are provided a method of manufacturing a semiconductor device, including:

(a) forming an oxide film on a substrate in the process chamber formed by a reaction tube and a manifold supporting the reaction tube by performing a cycle a predetermined number of times, the cycle including supplying a source gas to the substrate in the process chamber through a first nozzle disposed in the manifold and extending upward from the manifold to an inside of the reaction tube, and supplying an oxidizing gas to the substrate in the process chamber through a second nozzle disposed in the manifold and extending upward from the manifold to the inside of the reaction tube; and

(b) cleaning an inside of the process chamber after the step (a) is performed,

wherein the step (b) includes:

a first cleaning process of supplying a hydrogen fluoride gas into the reaction tube through the second nozzle; and

a second cleaning process of supplying a hydrogen fluoride gas onto an inner wall surface of the manifold through a third nozzle disposed in the manifold.

(Supplementary Note 17)

According to still another embodiment of the present invention, there is provided a substrate processing apparatus, including:

a process chamber formed by a reaction tube and a manifold supporting the reaction tube;

a source gas supply system configured to supply a source gas into the process chamber;

an oxidizing gas supply system configured to supply an oxidizing gas into the process chamber;

a hydrogen fluoride gas supply system configured to supply a hydrogen fluoride gas into the process chamber;

a first nozzle disposed in the manifold and extending upward from the manifold to an inside of the reaction tube;

a second nozzle disposed in the manifold and extending upward from the manifold to the inside of the reaction tube;

a third nozzle disposed in the manifold; and

a control unit configured to control the source gas supply system, the oxidizing gas supply system and the hydrogen fluoride gas supply system to perform: (a) forming an oxide film on a substrate in the process chamber by performing a cycle a predetermined number of times, the cycle including supplying the source gas to the substrate in the process chamber through the first nozzle and supplying the oxidizing gas to the substrate in the process chamber through the second nozzle; and (b) cleaning an inside of the process chamber after performing the step (a), wherein the step (b) includes a first cleaning process of supplying the hydrogen fluoride gas into the reaction tube through the second nozzle and a second cleaning process of supplying the hydrogen fluoride gas onto an inner wall surface of the manifold through the third nozzle.

(Supplementary Note 18)

According to yet another embodiment of the present invention, there are provided a program and a non-transitory computer-readable recording medium storing the program causing a computer to execute:

(a) forming an oxide film on a substrate in the process chamber formed by a reaction tube and a manifold supporting the reaction tube by performing a cycle a predetermined number of times, the cycle including supplying a source gas to the substrate in the process chamber through a first nozzle disposed in the manifold and extending upward from the manifold to an inside of the reaction tube, and supplying an oxidizing gas to the substrate in the process chamber through a second nozzle disposed in the manifold and extending upward from the manifold to the inside of the reaction tube; and

(b) cleaning an inside of the process chamber after the step (a) is performed,

wherein the step (b) includes:

a first cleaning process of supplying a hydrogen fluoride gas into the reaction tube through the second nozzle; and

a second cleaning process of supplying a hydrogen fluoride gas onto an inner wall surface of the manifold through a third nozzle disposed in the manifold.

Claims (11)

What is claimed is:

1. A substrate processing apparatus comprising:

a reaction tube configured to accommodate a substrate therein;

a manifold supporting the reaction tube;

a process chamber defined by the reaction tube and the manifold;

a cover portion configured to close an opening at a lower end of the manifold and face an entirety of an inner wall surface of the manifold in a circumferential direction of the inner wall surface;

a guide portion disposed at the cover portion to face the inner wall surface of the manifold;

a source gas supply system configured to supply a source gas into the process chamber via a first nozzle;

a reaction gas supply system configured to supply a reaction gas into the process chamber via a second nozzle; and

a third nozzle disposed at the manifold to supply a cleaning gas into a gap between the manifold and the guide portion,

wherein the guide portion has a clearance between an entirety of an upper end of the guide portion and the inner wall surface of the manifold.

2. The substrate processing apparatus ofclaim 1, wherein a gas supply hole of the third nozzle is lower than the upper end of the guide portion.

3. The substrate processing apparatus ofclaim 2, wherein the guide portion is disposed concentrically with the inner wall surface of the manifold.

4. The substrate processing apparatus ofclaim 3, wherein the guide portion comprises: a side surface portion facing the inner wall surface of the manifold; and an extending portion extending horizontally from the side surface portion toward the inner wall surface of the manifold.

5. The substrate processing apparatus ofclaim 4, wherein the extending portion comprises a slit.

6. The substrate processing apparatus ofclaim 5, wherein the extending portion extends from an upper end or a lower end of the side surface portion.

7. The substrate processing apparatus ofclaim 6, wherein the guide portion comprises a heat-resistant material including at least one of quartz and SiC.

8. The substrate processing apparatus ofclaim 7, wherein the reaction gas comprises an oxidizing gas.

9. The substrate processing apparatus ofclaim 8, wherein the cleaning gas comprises a hydrogen fluoride gas.

10. A guide portion of a substrate processing apparatus comprising: a reaction tube configured to accommodate a substrate therein; a manifold supporting the reaction tube; a process chamber defined by the reaction tube and the manifold; a source gas supply system configured to supply a source gas into the process chamber via a first nozzle; a reaction gas supply system configured to supply a reaction gas into the process chamber via a second nozzle; a cleaning gas supply system configured to supply a cleaning gas to the manifold via a third nozzle disposed at the manifold; and a cover portion configured to close an opening at a lower end of the manifold and face an entirety of an inner wall surface of the manifold in a circumferential direction of the inner wall surface, the guide portion, disposed at the cover portion, comprising:

a side surface portion facing the inner wall surface of the manifold to define a space with the manifold where the cleaning gas is supplied; and

an extending portion extending from the side surface portion toward the inner wall surface of the manifold,

wherein the guide portion has a clearance between an entirety of an upper end of the guide portion and the inner wall surface of the manifold.

11. The substrate processing apparatus ofclaim 1, wherein the clearance is configured t allow the cleaning gas supplied into the gap to escape from the gap to the process chamber therethrough.

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